Electrically driven metallo-organic assemblies: electrochromism and chiroptical properties

Abstract

The present disclosure relates to chiral materials and films comprising metal- coordinated organic complexes. Specifically, the invention provides compositions, derivative structures, and methods for the preparation of such materials in solution, as coatings, and in other forms. These films exhibit chiral properties allowing for tunable chiral-electrochromic capabilities for optoelectronic devices, and display technologies.

Description

ELECTRICALLY DRIVEN METALLO-ORGANIC ASSEMBLIES:ELECTROCHROMISM AND CHIROPTICAL PROPERTIESFIELD OF THE INVENTION

[0001] The presently disclosed subject matter relates to the field of chiral materials and films comprising metal-coordinated organic complexes, their derivative structures and methods to produce solutions, coatings and pixels comprising them.BACKGROUND

[0002] Rational design of stimuli -responsive materials (SRMs) is very attractive and desirable. Nevertheless, understanding and controlling the properties of such materials is a challenge. These “smart” materials, which can change color, modulate light, and other functionalities when stimulated by an external trigger, can be the solution for many challenges, ranging from sustainable energy to communication, information storage and information transfer. Among the different SRMs, there is the class of electrochromic materials. Electrochromism is the ability of a material to change its optical properties reversibly in response to an external applied potential. Developed herein are high-performance electrochromic materials that can be addressed electrochemically and used these materials on transparent electrodes as the heart of electrochromic devices. The solid-state configuration exhibits a practical combination of low- voltage operation, high redox-stability, high-contrast ratios, and short switching times. Moreover, electrochromic materials that are chiral, for the design of chiroptical switches or light modulators are shown. Surface-confined assemblies are designed and based on chiral electrochromic metallo-organic complexes, and shows how to manipulate and control their reaction with light, by oxidation and reduction of the assembly. Chiral anions are also used to create a variety of materials and films that derive therefrom. Various platforms were used such as palladium(II) pyridine coordination-chemistry to assemble well-defined metal complexes into functional thin films. The layers of these films are deposited using newly developed layer-by- layer (LbL) spin coating and spray-casting approaches. One aim is to introduce materials that exhibit both switchable chiral-optical and electrochromic properties. The preparation of enantiomerically pure metal complexes and the formation of electrochromic films that are chiral. As shown herein, the use of chiral anions is also employed to direct the chirality of various materials and their derivatives into structures such as films.

[0003] Provided herein are molecular-based thin films and corresponding solid-state devices.SUMMARY

[0004] In one embodiment the invention provides a chiral film comprising: chiral structures comprising at least one metal -coordinated organic complex; and at least one metal linker interspersed within the film.

[0005] In one embodiment the chiral structures comprise pi-pi stacking. In one embodiment the metal-coordinated organic complex comprises bipyridine-based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. In one embodiment the unsaturated moi eties are selected from: C=C, C=C, C=N, and N=N, or a combination thereof. In one embodiment the chiral structures are crystalline. In one embodiment the chiral structures are in a form selected from: sheets, folded sheets, rods, twisted rods, cuboidal, bowties, half bowties, cuboidal, pyramids, or a combination thereof. In one embodiment the film is electrochromic.

[0006] In one embodiment the at least one metal -coordinated organic complex is a polypyridyl complex.

[0007] In one embodiment the polypyridyl complex is represented by Formula I:whereinM is a transition metal selected from Mn, Fe, Co, Ni, Cu, Zn, Ti, C, Cr, Rh, or Ir; n is the formal oxidation state of the transition metal, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Ciojalkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl,heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai to Ae each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula I via R19R19 each independently is selected from a covalent bond, H2C-CH2, HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2-COO-, -CONH-, -CON(OH)-, -NR20-, - Si(R2o)2-, an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,Rxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.

[0008] In one embodiment the polypyridyl complex is represented by Formula II:wherein n is the formal oxidation state of Fe, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai, A3, and A5 each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula II via R19R19 each independently is selected from a covalent bond, H2C-CH2, cis / trans HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2 -COO-, -CONH-, -CON(OH)-, -NR20-, -Si(R2o)2- an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,Rxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Bi to B3 each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, - N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl,heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.

[0009] In one embodiment the chiral structures have a size ranging between 10 nm to 100 pm. In one embodiment the wherein the metal of the at least one metal linker is selected from the group consisting of Zn, Os, Ru, Fe, Pt, Pd, Ni, Ir, Rh, Co, Cu, Re, Tc, Mn, V, Nb, Ta, Hf, Zr, Cr, Mo, W, Ti, Sc, Ag, Au, and Y. In one embodiment the at least one metal linker is selected from: Na2PdCh, (SO3H-3-Py)2Pd(Cl)2, or a combination thereof.

[0010] In one embodiment the invention provides a device comprising: a substrate; the chiral film of the invention; an electrolyte disposed on the chiral film; an ion storage layer disposed on the electrolyte; and a counter electrode in contact with the ion storage layer.

[0011] In one embodiment the electrolyte is selected from: ACN / PC / PMMA / trifluoromethylsulfonamide lithium salt, polymethyl methacrylate (PMMA), propylene carbonate (PC), LiCF3SO3, LiBF4, Li2+2xZnl-xGeO4 (Li SICON), glassy lithium phosphorus oxynitride (LIPON), and LiClO4 or any combination thereof.

[0012] In one embodiment the ion storage layer comprises any of the following selected from: polymers, copolymers, metal-organic polymer, coordination polymer, molecular film, metallic coating, transparent conducting oxides, metal oxides, metal fluorides, metal nitrides, metal sulfides, nanocrystalline metal oxides, mixed metals oxides, redox-active species, carbon-based materials, graphene-based materials, buckminsterfullerenes, nanotubes, 2D materials, biomolecules, nanowires, polymethyl methacrylate (PMMA), benzocyclobutene (BCB) based polymers, poly(3,4-ethylenedioxythiophene), poly(styrenesulfonate), conjugated dithiolenes, polyelectrolytes, organic salts, inorganic salts, quinone-based compounds, viologen-based compounds, antimony-doped tin oxide (ATO), pyridine blue (PB), polyaniline, polypyrrole, lithium cobalt oxide, lithium cobalt oxide, indium tin oxide, fluorine doped tin oxide, niobium oxide, molybdenum oxide, zinc oxides, aluminum oxide, nickel oxides, ceric oxide, metal doped nickel oxides, lithium doped nickel oxides, lithium doped titanium oxides, polymetal oxides, nanoparticles, metallic nanoparticles, nickel hexacyanoferrate, iron hexacyanoferrate, lithium hexacyanoferrate, sodium hexacyanoferrate, manganese hexacyanomanganate, halogen-dopedmetal oxides, lithium sulfide, lithium garnet, lithium phosphorous oxynitride, lithium manganese oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, sodium nickel chloride and activated carbon.

[0013] In one embodiment the counter electrode comprises any of the following selected from: glass, doped glass, metal-oxide, indium tin oxide (ITO)-coated glass, fluorine-doped tin oxide (FTO)-coated class, silicon, doped silicon, zinc oxide (ZnO), Si(100), Si(l l l), SiO2, SiH, silicon carbide mirror, quartz, metal, metal oxide, mixture of metal and metal oxide, group IV elements, mica, graphite comprising intercalated metal cations, polymer, plastic, zeolite, clay, membrane, optical fiber, ceramic, metalized ceramic, alumina, electrically-conductive material, semiconductor, steel, and stainless steel, gold, silver, platinum, copper, zinc, aluminium or any combination thereof.

[0014] In one embodiment the chiral layer is in the form of an array of pixels and / or patterned on the substrate. In one embodiment the device further comprises a lamination. In one embodiment the chiral film is electrochromic.

[0015] In one embodiment the device is for use in any of the following: smart windows, electrochromic windows, smart mirrors, optical filters, frequency doubling devices, spatial light modulators, pulse shapers, displays, signs, plastic electronics, lenses, and sensors.

[0016] In one embodiment the invention provides a method of producing a chiral solution, the method comprising: providing a solution comprising at least one chiral anion; disposing at least one metal-coordinated organic complex in the solution thereby producing a chiral solution comprising chiral structures of the at least one metal-coordinated organic complex.

[0017] In one embodiment the solution comprises any of the following selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones and diethyl ether or any combination thereof.

[0018] In one embodiment the at least one chiral anion comprises a negatively charged functional group. In one embodiment the negatively charged functional group is selected from:phosphates (PO43), sulfonates (RS(=O)2O ), sulphates (SO4)2-, carboxylates (RCOO-), borates (R4B-) serinate ([C3H6NO3]-), alanine ([C3H7NO2]-), tartaric acid ([C4H6O6]2-), mandelic acid ([C8H8O3]-), aspartic acid ([C4H6NO4]-), glutamic acid ([C5H8NO4]-), methionine ([C5H11NO2S]-), phenylalanine ([C9H11NO2]-), camphorsulfonate ([C10H15O4S]-), isoleucine ([C6H13NO2]-), ibuprofen ([C13H17O2]-), leucine ([C6H13NO2]-), naproxen ([C14H13O3]-), valine ([C5H11NO2]-), serine ([C3H7NO3]-), cysteine ([C3H7NO2S]-), naproxenate ([C14H13O3]-), proline ([C5H9NO2]-), histidine ([C6H9N3O2]-), tyrosine ([C9H11NO3]-), glutamate ([C5H8NO4]-), tryptophan ([Cl 1H12N2O2]-), threonine ([C4H9NO3]-), L-Tartrate ([C4H4O6]2-), D-Tartrate ([C4H4O6]2-), phenylalaninate ([C9H10NO2]-), ibuprofenate ([C13H17O2]-), L-Malate ([C4H4O5]2-), D-Malate ([C4H4O5]2-), lactate ([C3H5O3]-), D-Lactate ([C3H5O3]-), mandelate ([C8H7O3]-), leucinate ([C6H13NO2]-), aspartate ([C4H5NO4]-), phenylglycinate ([C8H8NO2]-), camphorate ([C10H15O4]-), camphanate ([C10H15O4]-), methioninate ([C5H11NO2S]-), norbornane-2-carboxylate ([C7H1102]-), troponate ([C7H1102]-), cysteinate ([C3H6NO2S]-), alaninate ([C3H7NO2]-), isoleucinate ([C6H13NO2]-), valinate ([C5H11NO2]-), and tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene-l,2-diolato- K2Ol,O2)phosphorus(V) [(P(O2C6C14)3-)] (= TRISPHAT), or any combination thereof.

[0019] In one embodiment the at least one chiral anion comprises the deprotonated form of any of the following selected from: tartaric acid, mandelic acid, amino acids, lactic acid, camphor, sulfonic acid, or a combination thereof.

[0020] The method of claim 22 wherein the at least one chiral anion comprises any of the following selected from: chromophore, fluorophore, metal, boron-dipyrromethene (BODIPY), porphyrin, fluorene, azobenzene, stilbene, rhodamine, indocyanine, polycyclic aromatic hydrocarbons, at least one halide, electron withdrawing group, electron donating group, or a combination thereof.

[0021] In one embodiment the electron withdrawing group is selected from: fluorocarbons, aldehydes, halogens, carbonyl, cyanides, nitro, sulfonic acid, carboxylic acid, ester group, amide group, nitroso group, or a combination thereof.

[0022] In one embodiment the electron donating group is selected from: alkyl, allyl, vinyl, phenyl, alkylamino, alkoxy, amino, hydroxyl, thiol, ether, or a combination thereof.

[0023] In one embodiment the polycyclic aromatic hydrocarbons are selected from: naphthalene, biphenyl, fluorene, anthracene, phenanthrene, phenalene, tetracene, chrysene, triphenylene, pyrene, pentacene, perylene, benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene, benzo[c]fluorene.

[0024] In one embodiment the invention provides a chiral solution prepared by a method of the invention.

[0025] In one embodiment the invention provides a chiral solution comprising: a solution comprising at least one chiral anion; chiral structures dispersed within the solution; and wherein the chiral structures comprise at least one metal-coordinated organic complex.

[0026] In one embodiment the invention provides a method of producing an electrochromic chiral film, the method comprising: providing a substrate; depositing a linker layer comprising at least one metal linker; depositing a chiral solution comprising chiral structures and a chiral anion, wherein the chiral structures comprise at least one metal-coordinated organic complex; and repeating steps (b) and (c) until a desired thickness is reached, forming a chiral film.

[0027] In one embodiment the method further comprises at least partly removing the chiral anion by exchange with achiral counterions, and wherein the electrochromic chiral film remains chiral. In one embodiment the achiral counterions comprise any of the following selected from: PFe-, organic anions, pseudohalides, boron-based anions, hydride-based anions, halide anions, phosphorus-based fluoroanions, oxyanions, and oxide-based anions, or a combination thereof. In one embodiment the depositing is selected from: spin coating, dip coating, brush coating, roller coating, flow coating, drop casting, mill rod coating, chemical vapor phase deposition (CVD), roll-to-roll (R2R) processing, electropolymerization, printing, layer-by-layer deposition, organic powder coating, inkjet printing, spray coating, ultrasonic spray coating, blade-coating, physical vapor deposition (PVD), Meyer bar coating, or a combination thereof.

[0028] In one embodiment the at least one metal linker comprises a metal salt. In one embodiment the metal salt is a metal -based coordination complex.

[0029] In one embodiment the at least one metal linker has the general formula MXYL1L2; wherein M is metal;X is a halide counterion;Y is a halide counterion; andLi = L2 or Li L2;Li and L2 are one ligand with two binding groups wherein each binding group is the same or different.

[0030] In one embodiment the M is: zerovalent, monovalent, bivalent or trivalent. In one embodiment the M is selected from: Fe, Co, Zn, Ni, Pt and Pd. In one embodiment the at least one metal linker is selected from: PdCh, PdC12(CH3CN)2, PdC12(PhCN)2, PdCbfCxHn) where CsHu is cycloocta- 1,5-diene (cod) or abbreviated PdCh(cod), PdSO4, Pd(NO3)2, Pd(OAc)2, PdBr2, Pd(OSO2CF3)2, Pd(BF4)2,PtCl2, PdCl2(Sme2)2, PdBr2, PdBr2(CH3CN)2, PdBr2(PhCN)2, PdBr2(CsHi2) where CxHn is cycloocta-l,5-diene (cod) or abbreviated PdBr2(cod), PdSO4, Pd(NO3)2, Pd(OAc)2, PdBr2, Pd(OSO2CF3)2, Pd(BF4)2, PdCl2(olefm)nwith n = 1, 2 or 3, PdBr2(olefm)nwith n = 1, 2 or 3, PtC12(olefm)nwith n = 1, 2 or 3, PtBr2(olefm)nwith n = 1, 2 or 3, PtC12PtC12(CH3CN)2, PtC12(PhCN)2, PtC^CsHu) where CxHn is cycloocta-l,5-diene (cod) or abbreviated PtCl2(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtCl2, PtBr2(CH3CN)2, PtBr2(PhCN)2, PtBr2(CsHi2) where CxHn is cycloocta- 1,5-diene (cod) or abbreviated PtBr2(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtBr2, Pt(OSO2CF3)2, Pt(BF4)2, PtCl2(Sme2)2, PtBr2(Sme2)2, CuSO4, CuCl2, CU(OH)2, CU(NO3)2, Cu(Oac)2, CuBr2, Cu(OSO2CF3)2, Cu(BF4)2, Cu(C6H5CO2)2, NiCh, NiC12(CH3CN)2, NiC12(PhCN)2, NiC^CsHn) where CxHn is cycloocta-l,5-diene (cod) or abbreviated NiCl2(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2, Ni(BF4)2,NiCl2, NiC12(Sme2)2, NiBr2(CH3CN)2, NiBr2(PhCN)2, NiB^CsHn) where CsHn is cycloocta-1,5- diene (cod) or abbreviated NiBr2(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2, Ni(BF4)2, NiBr2(Sme2)2, NiC12(olefm)nwith n = 1, 2 or 3, NiBr2(olefm)nwith n = 1, 2 or 3, ZnCh, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBn, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBr2(olefm)nwith n = 1, 2 or 3, ZnCl2(olefin)n with n = 1, 2 or 3, K2PdCl4, K2PdCl6, Na2PdCl4, Na2PdCl6, K2PtCl4, K2PtCl6, Na2PtCl4, Na2PtCl6, FeCh, FeBr2, Fe(NO3)2, FeSO4, FeBr2(olefm)nwith n = 1, 2 or 3, FeC12(olefm)nwith n = 1, 2 or 3, Fe(OAc)2 or any combination thereof.

[0031] In one embodiment the metal-base of the metal-coordinated organic complex is selected from: Os, Fe, Ru, Mn, Cu, Zn, Ni, Cr, Ti, V, Ir, or Rh.

[0032] In one embodiment the method further comprises cleaning and drying the chiral film after at least one step. In one embodiment the cleaning is selected from: washing in organic solvents, sonication cleaning, immersion in solvents, UV-ozone cleaning, plasma etching, drying under a stream of gas, heating and vacuum drying or any combination thereof. In one embodiment the drying is selected from: drying under a stream of gas, annealing, heating and vacuum drying, or any combination thereof.

[0033] In one embodiment the invention provides a method of producing a chiral solution, the method comprising:providing a solvent; disposing at least one metal-coordinated organic complex in the solvent, producing an approximately racemic solution; providing a chiral seed comprising a metal-coordinated organic complex; and disposing the chiral seed into the racemic solution thereby producing the chiral solution comprising chiral structures formed from the at least one metal- coordinated organic complex.

[0034] In one embodiment the solvent is selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2- pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones, and diethyl ether or any combination thereof.

[0035] In one embodiment the racemic solution has a concentration ranging between 0.1 to 10 mM.

[0036] In one embodiment the chiral seed is selected from: right-handed chiral seed to produce a right-handed chiral solution; or left-handed chiral seed to produce a left-handed chiral solution.

[0037] In one embodiment the chiral seed is in the form of an aggregate, nanoparticle, crystal, flake, film or a combination thereof.

[0038] In one embodiment the chiral seed has a size ranging between 10 nm to 10 pm. In one embodiment the invention provides a chiral solution produced by method of chiral seeding.BRIEF DESCRIPTION OF THE DRAWINGS

[0039] To better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0040] Figures 1A-1B show molecular structures of the electrochromic polypyridyl complexes 1-4.

[0041] Figure 2 shows a schematic representation of the spontaneous formation of chiral nanostructures with random handedness from racemic solution, versus the possibility ofcontrolling the handedness of the nanostructures using seeding. Reversible disaggregating the nanostructures is also demonstrated by agitation. The molecular structure of complex 2 lacks its charge notation (2+) and two hexafluorophosphate (PFe') counter ions for clarity reasons.

[0042] Figure 3 shows Self-Propagating Molecular Assembly (SPMA). The coordinationbased structures are formed on a covalently bound monolayer by iterative deposition of metal- polypyridyl complexes (4) and PdCh. Other metal salts can be used as well.

[0043] Figure 4 shows the fabrication of the electrochromic molecular assemblies (MAs). The MAs were formed by depositing alternating layers of PdCh and complexes 1-4, or a combination thereof by spin-coating (n = 2-18). Transparent conductive oxides (TCOs) on glass and polyethylene terephthalate (PET) were used as substrates.

[0044] Figure 5 shows the fabrication process of electrochromic molecular assemblies (MAs) by ultrasonic spray-coating. The MAs were formed by depositing PdCh(PhCN)2 and complexes 1 or 2 using two automatic spray guns, (MAI is not drawn). Transparent conductive oxides (TCOs) on glass and polyethylene terephthalate) (PET) were used as substrates (2 cmz2 cm or 6 cm x 6 cm).

[0045] Figures 6A-6C show examples of three molecules used in the present invention.

[0046] Figure 7 shows a schematic representation of molecular-assemblies (MAs) consisting of polypyridyl complexes 1-4 cross-linked with palladium dichloride on a transparent conductive oxide (TCO). For simplicity, the structure of complex 2 is not drawn.

[0047] Figures 8A-8E shows the surface characterization of [MAI | FTO / glass] after 18 deposition cycles. Figure 8A shows the ex-situ absorption spectra recorded during the formation of MAI by alternating deposition cycles involving PdCh(PhCN)2 and complex 1. A bare FTO substrate was used for the baseline (black). Inset: absorbance intensity of the MLCT band (2max = 573 nm) vs. the number of deposition cycles showing a linear growth behavior. Figure 8B shows normalized X-ray photoelectron spectroscopy (XPS) spectra showing the Fe2+2p, N Is and Pd2+3d regions. Figure 8C shows a photograph of a 6 cm * 6 cm FTO / glass substrate coated with MAI. Figure 8D shows SEM images showing the cross-section of [MAI | FTO / glass]; milled by 30 keV Ga+FIB. The Pt coating was used to prevent ion beam damage. Magnification of the area marked in the SEM image on the left is magnified in an inset on the top-right; the corresponding schematic representation of MAI after Pt coating is shown on the bottom right. Figure 8E shows a representative AFM topography image. Figure 8F demonstrates the flexibility of the substrate of Figure 8C.

[0048] Figures 9A and 9B show the electrochemical characterization of [MAI | FTO / glass] after 18 deposition cycles. Figure 9A shows the cyclic voltammograms (CVs) of the 1stcycle(black trace) and the 1600thcycle (red trace) of [MAI | FTO / glass], The CVs were recorded at a scan rate of 0.1 V / s in 0.1 M TBAPFe / ACN. Figure 9B shows the peak current dependence of scan rates (0.01-1.0 V / sec) extracted from the corresponding CVs. Exponential and linear correlations between peak current and scan rate (left) and the square root of the scan rate (right), respectively, during oxidation (top) or reduction (bottom) (R2> 0.99 for all fits)

[0049] Figures 10A and 10B show the spectroelectrochemical (SEC) performance of MAI on FTO / glass in an electrolyte solution. Figure 10A shows the absorption spectra corresponding to two consecutive oxidation and reduction cycles of MAI. Bare FTO substrate was used for the baseline (black). Insets: Dependence of the contrast ratio (AT) on the switching time. Figure 10B shows photographs (top) of the colored and the bleached states of MAI and Spectroelectrochemistry (SEC), (bottom), using double-potential steps of 0.4-1.6 V (2max = 573 nm). The two traces represent the spectroelectrochemical stability of MAI.

[0050] Figures 11A-11C show photographs of MA-coated transparent conductive oxides (TCOs) (2 cm x 2 cm and 6 cm x 6 cm): Figure 11A shows [MA2 | FTO / glass 10 Q / n], Figure 11B shows [MAI | FTO / glass 10 Q / n] and Figure 11C shows [MA2 | ITO / PET 30 Q / n],

[0051] Figures 12A-12E show the spectroelectrochemical (SEC) performance of an electrochromic device (ECD) based on [MAl|FTO / glass] as the working electrode and [PEDOT:PSS|FTO / glass] as the counter electrode (CE). Figure 12A shows a schematic representation of the MA1-ECD. Figure 12B shows photographs of the colored and bleached states of MA1-ECD (1.7 cm x 1.3 cm), initially and after 1500 redox cycles (-1.8 to +2.8 V). Figure 12C shows chronoamperometric (CA) stability measurements using double potential steps: -1.8 to +2.8 V. Figure 12D shows absorption spectra corresponding to two consecutive oxidation and reduction cycles (-1.5 to +3.0 V). Bare FTO substrates were used for the baseline (black). Figure 12E shows SEC stability measurements at +ma\ = 578 nm using double potential steps: -1.5 to +3.0 V.

[0052] Figures 13A-13F show a structural analysis of 2-nanostructures by scanning electron microscopy (SEM). Figures 13A-13C show images of the bow-tie like structures. Figure 13D shows a zoomed-out image showing the densified areas of the bow-tie like structures, where in the center of the image, relatively spacious area is shown, which contained the twisted rods structures. Figures 13E-13F show a zoomed in images of the twisted rods structures.

[0053] Figures 14A-14C show a structural analysis of 2-nanostructures. Figures 14A-14B show atomic force microscopy (AFM) images. Figure 14C shows a cryo-TEM image of 2 in MeOH / DCM (1 / 1 v / v) solution, 0.6 mM. The dotted line highlights the bow-tie like structure contour.

[0054] Figures 15A-15E show transmission electron microscope (TEM) imaging and electron diffraction. Figure 15A shows TEM images of twisted rod like 2-nanostructures. Figure 15B shows Scanning TEM annular dark-field imaging (STEM ADF) of region of interest (ROI). Inset: virtual dark-field magnification of the ROI. Figure 15C shows nano-diffraction of the selected area marked in the inset of Figure 15B. Figure 15D shows packing representation of the single-crystal structure of 2-A and 2-A isomers. Space group: P2(l) / c. The crystal structure is displayed in ORTEP views using thermal ellipsoids set at the 50% probability level. Hydrogen atoms and PFe- anions are omitted for clarity. Color code: black, carbon; blue, nitrogen; yellow, iron. Figure 15E shows X-ray-based analysis of the same viewing direction as the electron diffraction in Figure 15C.

[0055] Figure 16 shows computational calculations of relative energies for 2- aggregates, being the most energetically favored orientation of two 2 molecules.

[0056] Figure 17A shows the schematic representation of complexes 2 and 2’ and 4 and 4’ (as related to the polypyridyl complexes 1-8 of Figures 6A-6C). Figure 17B shows the molar ellipticity of 0.6 mM solutions of complexes 2, 2’ and 4, 4’, in ACN. The spectra on the top left panel stand for two identical independent solutions of 2, while the spectra on the bottom left panel stand for two identical independent solutions of 4. All the measurements were conducted in a quartz cuvette.

[0057] Figure 18A shows the molar ellipticity of 0.6 mM solutions of complexes 3-4, 7-10, in ACN. Figure 18B shows the absorbance spectra of 0.6 mM solutions of complexes 3-4, in ACN. All the measurements were conducted in a quartz cuvette.

[0058] Figure 19A shows single crystal x-ray analysis of complex 2’. Packing representation of the single-crystal structure of 2’. Space group: P-1. The crystal structures are displayed in ORTEP views using thermal ellipsoids set at the 50% probability level. Hydrogen atoms and PFe” anions are omitted for clarity. Color code: black, carbon; blue, nitrogen; yellow, iron. Figures 19B-19D show scanning electron microscopy (SEM) images of complex 2’, showing no aggregation. Figure 19D is a magnified SEM image of Figure 19C.

[0059] Figures 20A-20C show the effect of agitation on 2-nanostructures handedness. Figure 18A shows the molar ellipticity at = 589 nm versus the experiment number (Figure 20A) when no agitation was applied; (Figure 20B) for two independent samples (squares) and (up triangles), that underwent 10 s sonication cycles and (Figure 20C) the two independent samples (circles) and (down triangles), that underwent 10 s external stirring. The stirring was performed using a table-top shaker (IKA® Lab Dancer, 100 - 240 V), with no use of a magnet. All the measurements were conducted in a quartz cuvette.

[0060] Figures 21A and 21B show the reformation of 2-nanostructures after agitation. Dynamic light scattering (DLS) spectra of solution of complex 2 (0.6 mM, 2 mL), taken before (black trace), and after 10 sec of sonication. Legend: Immediately (red trace), 5 min (blue trace), 10 min (green trace), 15 min (purple trace), and 20 min (orange trace) after sonication. All the measurements were conducted in a 1 cm quartz cuvette.

[0061] Figures 22A-22C show the control of 2-nanostructures handedness by seeding. Figure 20A shows the statistical distribution of molar ellipticity (2 = 589 nm) among 24 independent samples of 0.6 mM ACN solution of complex 2. Figure 22B shows the molar ellipticity (2 = 589 nm among 10 independent samples of 0.6 mM ACN solution of complex 2 that were prepared in the presence of a negative seed. Figure 22C shows the molar ellipticity (2 = 589 nm among 10 independent samples of 0.6 mM ACN solution of complex 2 that were prepared in the presence of a positive seed. All the measurements were conducted in a quartz cuvette.

[0062] Figures 23A-23E shows cryogenic transmission electron microscopy (Cryo-TEM) images of folded 2D sheets and the final bow-tie morphology of 2-nanostructures in MeOH / DCM (1 / 1 v / v) solution, 0.6 mM. Figure 23E is a magnification of the area marked in Figure 23D. The dotted lines highlight the structural features. The scale bars in Figure 23A-23E are 100 nm.

[0063] Figure 24 shows a schematic representation of one step by step formation process of the chiral structures.

[0064] Figures 25A-25B show the effect of sample orientation. Figure 25A shows a schematic sketch to illustrate the sample rotation with the propagation direction of the light beam as z-axis. Figure 25B shows the CD spectra of MA4 at four different orientations: 0 in-plane (pink trace); 90 in-plane (blue trace); 90 out-of-plane (green trace); 0 out-of-plane (orange trace); and its quaternary sum (grey trace).

[0065] Figures 26A-26D show the optical properties of MA2, MA2’, MA4 and MA4’ on FTO substrates. Figure 26A-26B show optical absorption of (Figure 26A) complex 2 (grey and turquoise traces), and complex 2’ (pink trace); and (Figure 26B) complex 4 (red and bordeaux traces), and complex 4’ (green trace). The baseline (black trace) is the absorbance of bare FTO substrates. Figure 26C-26D show corresponding circular dichroism (CD) spectra of (Figure 26C) complex 2 (grey and turquoise traces), and complex 2’ (pink trace); and (Figure 26D) complex 4 (red and bordeaux traces), and complex 4’ (green trace). The baseline (black trace) is the CD of a bare FTO substrate.

[0066] Figures 27A-27B shows the elemental composition of MA2’ and MA4’ on FTO / glass. (Figure 27A-27B) Normalized X-ray photoelectron spectroscopy (XPS) spectra of MA2’ and MA4’ showing the Fe2+2p, Os2+4f, N Is and Pd2+3d bands. Figure 27C shows the XPS-derived elemental ratios for MA2’ (M=Fe) and MA4’ (M=Os) at two take-off angles.

[0067] Figures 28A-28D show the structural characterizations of MA2’ and MA4’ on FTO / glass. Figure 28A-28B show representative AFM topography images of MA2’ (Figure 28A) and MA4’ (Figure 28B) Figure 28C-28D show SEM image showing the cross section of MA2‘ (Figure 28C) and MA4’ (Figure 28D), that were milled by 30 keV Ga+ focused ion beam (FIB). Pt coating is used to prevent beam damage. Scale bar: 2 / / m.

[0068] Figures 29A-29F show electrochemical characterizations of MA2’ on FTO / glass substrate. Figure 29A shows cyclic voltammogram (CV) of MA2’. The CV was recorded at a scan rate of 0.1 V / s in 0.1M TBAPFe / acetonitrile (ACN). Figure 29B shows dependence of the peak current on the scan rate (0.01-0.4 V / s) extracted from the corresponding CVs. Exponential and linear correlations between the peak current and the scan rate (left) and between the peak current and the square root of the scan rate (right), respectively, during oxidation (top) and reduction (bottom) (R2> 0.98 for all fits). Figure 29C shows SEC at different switching times. The SEC was recorded at a potential window of 0.2 V to 1.8 V, on a 2 cm * 2 cm film, using 0.1 M TBAPFe / ACN electrolyte solution. Figure 29D shows exponential dependence of the contrast ratio (AT) on the switching time (R2> 0.99). Figure 29E shows SEC stability at switching time of 20 s. The SEC was recorded at a potential window of 0.2 V to 1.8 V, on a 2 cm * 2 cm film, using 0.1 M TBAPFe / ACN electrolyte solution. Figure 29F shows dependence of the contrast ratio (AT) on the number of switching cycles.

[0069] Figures 30A-30F shows the electrochemical characterizations of MA4’ on FTO / glass substrate. Figure 30A shows cyclic voltammogram (CV) of MA4’. The CV was recorded at a scan rate of 0.1 V / s in 0.1M TBAPFe / acetonitrile (ACN). Figure 30B shows dependence of the peak current on the scan rate (0.01-1.0 V / s) extracted from the corresponding CVs. Exponential and linear correlations between the peak current and the scan rate (left) and between the peak current and the square root of the scan rate (right), respectively, during oxidation (top) and reduction (bottom) (R2> 0.99 for all fits). Figure 30C shows SEC at different switching times. The SEC was recorded at a potential window of 0.2 V to 1.4 V, using 0.1 M TBAPFe / ACN electrolyte solution. Figure 30D shows exponential dependence of the contrast ratio (AT) on the switching time (R2> 0.99). Figure 30E shows SEC stability at switching time of 5 s. The SEC was recorded at a potential window of 0.2 V to 1.4 V, using 0.1 M TBAPFe / ACN electrolytesolution. Figure 30F shows dependence of the contrast ratio (AT) on the number of switching cycles.

[0070] Figures 31A-31F show the spectroelectrochemical (SEC) performance of molecular assemblies MA2, MA2’, MA4 and MA4’ on FTO / glass in an electrolyte solution. (Figure 31A- 31B, Figure 31D-31E) Absorption spectra (top) and CD spectra (bottom) corresponding to two consecutive oxidation and reduction cycles of (Figure 31A) MA2, (Figure 31B) MA2’, (Figure 31C) MA4, and (Figure 31D) MA4’. Bare FTO substrates were used for the baselines (black traces). (Figure 31C and Figure 31F) Photographs of the colored and bleached states of (Figure 31C) top: MA2; bottom: MA2’, and (Figure 31F) top: MA4; bottom: MA4’.

[0071] Figures 32A-32D show chiroptical switching (i.e., intensity of the optical signal related to the chirality) of MA2, MA2’, MA4 and MA4’ on FTO / glass (namely, the intensity of the optical signal related to the chirality). Figures 32A and 32B show SEC and Figures 32C and 32D show Polarized Light Spectroelectrochemistry (PL-SEC), using double-potential steps of (Figure 32A-32B) 0.4 V to 1.8 V (MA2, / .max = 589 nm, gray traces), and 0.4 V to 1.6 V (MA2’, / .max = 535 nm, pink traces); (Figure 32C-32D) 0.4 V to 1.2 V (MA4, Zmax = 510 nm, red traces), and 0.2 V to 1.4 V (MA4’, Amax = 500 nm, green traces). The data was normalized so that the absorbance and CD values of the oxidized states are zero.

[0072] Figures 33A-33B show a color palette of the molecular assemblies (MAs) and corresponding RGB color space demonstrating the color diversity and intensity. Figure 33A show the color diversity is demonstrated by depositing alternating layers of a palladium salt and complexes 1-4, or a combination thereof. The color intensity is a function of the number of deposition cycles (shown above are the palettes). Figure 33B shows the two ellipsoids in the RGB color space indicate the molecular assemblies (MAs) with purple and red tones according to standard color palette definitions.

[0073] Figure 34 shows the synthetic route to prepare complex 1 (A) - TRISPHAT (A) from ligand LI.

[0074] Figures 35A-35B show Delta, A, (Figure 35A) and Lambda, A, (Figure 35B) enantiomers of complex 2. Carbon (gray), nitrogen (blue), and iron (orange) are shown. The vinylpyridyl groups enable the formation of robust 3D networks with metal salts.

[0075] Figure 36 shows structures of A (left) and A (right) [Fe(dimethyl-bpy)3]2+. The lability of the Fe-N bonds results in enantiomerization of the A and A configurations via the Ray-Dutt twist. The red arrows (center) denote the twisting of the ligands around the metal-ligand axis.

[0076] Figures 37A-37E shows examples of enantiopure counterions that are used in the invention.

[0077] Figures 38A-38F shows a schematic of electrically driven optical switches based on isostructural iron and ruthenium polypyridyl complexes. Figures 38A-38D show the combination of devices fabricated with films of opposite chirality which result upon applying a potential in an optical output, which is recorded by UV / Vis and Circular Dichroism (CD) spectroscopy. The inset table in Figure 38A shows the output of each configuration (from Figure 38A to Figure 38D).

[0078] Figures 39A-39C show pixelation and security printing applications.

[0079] Figure 40A shows solution chemistry of circular dichroism (CD) spectroscopy for chiral solutions comprising complexes. Figure 40B shows solution chemistry of UV / Vis spectroscopy for chiral solutions comprising complexes.

[0080] Figure 41A shows solution chemistry circular dichroism (CD) spectroscopy for chiral and non-chiral solutions comprising Fe-complexes. Figure 41B shows solution chemistry UV / vis spectroscopy for chiral and non-chiral solutions comprising Fe-complexes. Figures 41A and 41B show CD and UV / vis spectroscopy for the Fe-complexes shown in Figure 41C. Figure 41C shows the contribution of the presence of ‘arms’ and C=C bonds in the arms that contribute to the chirality of the solution.

[0081] Figure 42A shows a schematic for anion exchange during electrochemistry. Figure 42B shows the spectroelectrochemisty (SEC) of chiral MA / FTO / glass samples; the chirality is maintained after electrochemical cycling. Figure 42C shows a corresponding Table of XPS results following the anion exchange shown in Figures 42A and Figure 42B.

[0082] Figure 43A-43E shows results SEC results for electrochromic chiral films with ion exchange. Figure 43A shows electrochemistry. Figure 43B shows UV / vis spectra. Figure 43C shows changes in CD with layer incremental layer deposition. Figure 43D shows chiroptical switching. Figure 43E shows cycling for chiral films.

[0083] Figures 44A-44B show UV-Vis and Circular dichroism (CD) of the chiral complex: 1(A) - TRISPHAT (A).

[0084] Figure 45A-45F show CD spectra of MA / FTO / glass. Figure 45A shows UV-Vis and Figure 45B shows Circular dichroism (CD) of the chiral MA|FTO / glass, and Figure 45C shows a comparison of Circular dichroism (CD) in solution and on the surface. Figures 45D shows transmittance for chiral films and switching cycles. Figure 45E shows chioptical switching under polarized light. Figure 45F shows CD spectra before / after cycling. Figures 45G-45I show SEC results for laminated devices of chiral MA / FTO / glass. Figure 45G shows electrochemistry. Figure 45H shows CD spectra. Figure 451 shows transmittance as a function of cycling.

[0085] Figures 46A-46B show the characterization of UV-vis (Figure 46A) and Circular dichroism (CD, Figure 46B) of the chiral complex 1(A) - TRISPHAT (A) in different solvents.

[0086] For simplicity and clarity of illustration, elements shown in the figures are not necessarily drawn to scale, and the dimensions of some elements may be exaggerated relative to other elements. In addition, reference numerals may be repeated among the figures to indicate corresponding or analogous elements.DETAILED DESCRIPTIONPolypyridyl Complexes

[0087] Polypyridyl complexes are coordination complexes composed of a metal center and a polypyridyl ligand. Polypyridine ligands are multidentate ligands that confer characteristic properties to the metal complexes that they form. Coordination complexes are known for their defined electrochemical, photochemical, and photophysical properties. Coordinatively saturated coordination complexes are relatively robust materials, which are generally not easily affected by air and high temperatures, with intense coloration due to their metal-to-ligand charge transfer (MLCT). All of the above, and the fact that their properties can be easily tuned by the choice of the metal center and their ligands design, make them attractive functional materials.

[0088] The present disclosure provides a series of isostructural complexes, having iron, osmium, ruthenium and cobalt as the metal centers, and bipyridine-based conjugated ligands, with pyridine groups in the periphery of the ligands, for further coordination (Figures 1A-1B).

[0089] Complexes 1-4 are octahedral complexes. Their geometry dictates the presence of geometrical and optical isomers. When a complex contains asymmetrical ligands (e.g. complexes 1, 3 and 4), it can exist as the facial or the meridional isomer. These isomers differ in the relative orientation of their ligands. If the complex contains symmetrical ligands (e.g. complex 2), it can exist as the A or the A isomer. Racemic mixture of the A and the A isomers of a complex will not be optically active, whereas enantio-pure solutions of the complex expect to show optical activity.Spontaneous Symmetry Breaking

[0090] Chiral symmetry breaking is the phenomenon in which an achiral substance is converted to a chiral substance, and an enantiomeric substance predominates. Two processes of forming enantiomeric substances are energetically identical, and both enantiomers are generally formed in equivalent amounts. Chiral symmetry breaking occurs when a physical or chemicalprocess, with no preference for the production of one or other enantiomer, spontaneously generates a large excess of one of the two enantiomers: (L), left-handed or (D), right handed.Formation of Chiral Supramolecular Assemblies in Solution

[0091] Chiral materials have been of great interest for many years, as they are related to research fields ranging from the study of life origins, through biological structure and function, up to studying and utilizing their unique optical properties for photonic applications. Usually, chirality of a system is determined by the chirality of the building blocks that the system is composed of. However, counting on chiral building blocks forces the exhausting and not trivial development of separation processes. Hence, it is of great interest to understand how to generate chiral systems from achiral building blocks or racemic mixture of chiral molecules. In comparison with the rich knowledge that has been gathered regarding chiral self-assembly, less is known about the supramolecular chirality of self-assembled systems based on achiral or racemic building blocks, although these systems are also very important for the fundamental symmetry breaking among self-assembly processes. In various circumstances the chirality of a system is a result of the supramolecular arrangement, and not enantiomeric excess or enantio- pure composition and therefore, the handedness of such supramolecular structures is random. Meaning, positive, negative and zero circular dichroism (CD) signals are observed. However, if a system is self-assembled via secondary nucleation mechanism, also known as “sergeant and soldiers” mechanism, then the final structure is expected to adopt the handedness of the initial seed that is formed. In this case, there is spontaneous symmetry breaking, and the system is optically active. Other possible pathway that leads to symmetry breaking is autocatalysis. It is noted that even small chiral biases can lead to large enantiomeric excess.

[0092] Understanding the mechanism of formation can lead to possible control over the handedness of the structures, utilizing its mechanistic pathway, i.e. by using pre-formed seeds during the growth. These chiral supramolecular systems are attractive as they can be the active element for chiral recognition, enantiomeric resolutions and optoelectronic devices.

[0093] It is shown that octahedral iron, osmium or ruthenium-based complexes, in racemic solutions thereof, tend to aggregate in a chiral manner to form chiral nanostructures. The formation of these nanostructures originates in TT-TC stacking interactions between ligands of adjacent molecules, to form small crystalline units, which later come closer and aggregate to sheets, and twisted chiral structures. The chirality of the formed structures is random, and reversible. The intermol ecular interactions between adjacent molecules are breakable upon applying external physical forces. The handedness of the fully formed structures can be controlled by seeding, which might indicate that the aggregation process is following thesecondary nucleation mechanism (Figure 2). As will be shown in the examples and corresponding figures, some nanostructures were observed using AFM, SEM, TEM and cryo- TEM. Solutions of these structures are optically active and are investigated by CD spectroscopy.Supramolecular Architectures as Surface-modified Electrodes

[0094] The formation of well-organized structures in solution, as well as on surfaces is of high importance. Several methods of deposition of organic materials on surfaces will be shown, including Langmuir-Blodgett methods, dip coating, printing, printing, spin coating and spray casting among others.

[0095] In the process of deposition on surfaces, layer-by-layer (LbL) approach is advantageous since it allows studying the kinetics of the growth process, as well as control over the physicochemical properties (e.g., thickness, absorption intensity, and electrochemical response) by optimizing the number of deposition cycles. In the LbL procedure, two or more components are deposited sequentially and repeatedly, to elongate the multilayers in a controlled fashion.

[0096] It is noted that the deposition of polypyridyl complexes of cobalt, iron, ruthenium, osmium, and a salt of palladium dichloride from solution results in linear and exponentially growing molecular assemblies. The overall reaction is essentially a three-component process, in which the self-propagating molecular assemblies (SPMAs) store excess of the <f palladium salt. The palladium salt is used to coordinatively bind polypyridyl complexes from solution on to the surface of the assembly (Figure 3). In various embodiments the metal center of Figure 3 can include any of the other metals disclosed herein. For example, PdCh(PhCN)2 and PdCh can both be used.Electrochromic Materials

[0097] It is demonstrated herein that a highly versatile fabrication process, based on spin coating that allows the formation of homogenous, high-chromophore density coatings on transparent conductive metal-oxides (Figure 4). The versatility is shown by both the intensity and diversity of colors that are achieved by the incorporation of different chromophores in a single assembly. These coatings are deeply colored in their ground state and become transparent upon electrochemical oxidation. Also demonstrate herein is the design of an electrochromic coating that exhibits a col or-to-col or transition. Some of these nanoscale thick coatings (210-300 nm) have high coloration efficiencies up to 473 cm2 / C, switching stabilities (up to -4000 cycles) and ON / OFF ratios as high as 64 %. Furthermore, low-voltage operable (-2.5 V to +3 V) rigidand flexible devices have been fabricated using the new metallo-organic coatings as the functional switching element.

[0098] Industrial scaling of metallo-organic films and devices is a challenging task and requires the fulfillment of many parameters, including scalability, a minimum number of deposition steps, high material utilization, and fast kinetics to allow for high-throughput production. Conferring compatibility of scalable coating procedures to existing production facilities will be a significant advantage. In this respect, spray coating is a promising approach that can be combined with industrially important roll-to-roll (R2R) coating processes.

[0099] It is shows herein that the on-surface formation of functional metallo-organic assemblies using a fully automated spray-coating procedure (Figure 5). The formation of such metallo-organic assemblies by iterative spray-coating is not obvious since it requires a rearrangement on the surface to form a polymeric coordination network. The colorful and uniform assemblies have submicron thicknesses, covering surface areas as large as 100 cm2, while having electrochemically addressable iron centers (Fe2+ / 3+). The electrochromic properties of the spray-coated assemblies were evaluated in laminated device architectures with large optical windows. The use of a conducting polymer, PEDOT:PSS, as a charge-storage layer (90 ± 25 nm) resulted in devices that exhibit large changes in color intensity between bleached and colored states with ATmax = 40-50% at zma\ = 598 nm (gray) or zma= 578 nm (purple). These ECDs were reversibly addressed up to 1500 redox cycles. The usage of gold-coated copper grids on PET as a counter electrode resulted in a significant drop of the potential window (AE) by 4.5-2.5 V. No potential is required to maintain the colored state.Chiroptical Switches[000100] Chiroptical switches refer to materials whose optical properties, e.g., circular birefringence and circular dichroism, can be reversibly modulated under external stimuli such as light irradiation, heat, pH, chemicals, and electric fields. In one embodiment the chiroptical switching relates to the intensity of the optical signal related to the chirality. In one embodiment, “chiroptical switching” refers to a change in the chiroptical properties of a material in response to an external stimulus. In one embodiment the chiroptical switching is irreversible. In one embodiment the chiroptical switching is reversible. Chiroptical properties are optical properties that are sensitive to the chirality (handedness) of molecules. These properties include circular dichroism (CD), optical rotatory dispersion (ORD), and circularly polarized luminescence (CPL), or combinations thereof.[000101] In one embodiment, the chiroptical switch does not change chirality but the amount of absorbed polarized light is varied under at least one external stimulus. In one embodiment, thechiroptical switch does not change chirality but the amount of transmitted light is varied under at least one external stimulus. In one embodiment, the chiroptical switch does not change chirality but the amount of reflected light is varied under at least one external stimulus.[000102] These materials can find applications in the fields of photonics, data storage, optoelectronic devices etc. Throughout the years, many works have been published, covering the area of light activated chiroptical switches, thanks to the large amount of information that is known in this field. In contrast, electrically activated systems are relatively less studied, although they are much more advantageous, as many current technologies are based on electrically, rather than optically, induced changes. One class of electrically activated systems is the class of electrochromic materials. Electrochromism (EC) is the ability of a material to reversibly modulate its optical response via an electrochemical redox process. Electrochromic materials are characterized with drastic changes in absorption, which can be utilized to achieve efficient chiroptical switches.[000103] Demonstrated herein is the fabrication of electrochromic chiral films, from racemic mixtures of metallo-organic compounds. It is noted that racemic solutions of complex 2 or 4 contain self-assembled chiral nanostructures, thanks to the extended 7t-system of the vinyl- pyridine moieties. In addition, it is noted that the hydrogenated forms of these complexes do not tend to aggregate, and therefore the solution thereof is not optically active. Demonstrated herein is the preservation of the chiral features of the nanostructures that are in solutions of complexes 2 or 4, while spin-coating them on transparent conducting oxides (TCO) to form chiral films. To confirm that the source of chirality is indeed the conjugation nature of the complex ligands, control systems of spin-coated films have been studied, composed of the hydrogenated forms of complex 2, complex 2’; or of complex 4, complex 4’. These hydrogenated molecular assemblies, MA2’ and MA4’, are not expected to be chiral, as their components lack the conjugated systems of the ligands arms. The response of MA2 to an applied potential when investigated under circularly polarized light was compared to the response of MA2’: while both complexes, MA2 and MA2’ show strong electrochromic effect, only MA2 shows strong changes in its CD spectrum upon oxidation and reduction. The same was observed for MA4 versus MA4’. By studying these two systems, it is shown that the formation of chiral films composed of racemic solutions of 2 or 4, is independent of the metal center of the complex (iron versus osmium) or on the structure of the ligand (one arm asymmetric ligand versus symmetric two arms ligand), as long as the ligand is conjugated.Discussion[000104] Using four isostructural redox-active complexes consisting of the iron-ruthenium- osmium triad and two derivatives of organic ligands, electroactive materials have been introduced, which obtain excellent electrochromic properties. Versatile assembly methods are introduced and based on spin-coating and spray-casting to generate diversely colored nanoscale coatings, whose color intensities can be readily controlled by the number of deposition cycles or by applying a potential (Figures 33A-33B).[000105] The materials homogeneously cover the relatively rough surface of metal -oxide substrates up to 10 cm x 10 cm, without detectable electrical short circuits. This spin-coating approach is about 7-8 fold faster than Layer-by-Layer dip-coating methods that involve the use of densely packed organic monolayers covalently immobilized on the metal-oxide coated electrodes. These monolayers hamper efficient electrons transfer processes, thereby limiting the electrochromic characteristics of the metallo-organic assemblies. The coatings reported here are about 7-fold thicker than common films, and have a high chromophore density, and therefore have considerably lower optical transparency in the ground state while exhibiting a better optical transparency in the oxidized state.[000106] Regarding chirality, it has been found that the molecular structures of complexes 1-4, having extended 7t-system in the ligands arms, allow the formation of chiral nanostructures, by exploiting TT-TC interactions between adjacent ligands arms. These chiral nanostructures give rise to CD signals for racemic mixtures of complexes 1-4. Moreover, it has been found that forming films by spin-coating these complexes on TCOs, allows the preservation of the chiral nanostructures that are formed in solution, and results in the formation of chiral films. These chiral films obtain CD strong signals, which can be modified by applying external field. Switching the films between their oxidized and reduced states give rise to strong contrast ratio, which can allow these films to act as chiroptical switches. As shown in the examples, the CD signal, as well as its UV / Vis signal, can be modified by external stimuli, at the solid state, as a basis for electrically driven optical switches and devices.Chiral films of the invention[000107] In some embodiments the invention provides a chiral film comprising structures which comprise of at least one metal -coordinated organic complex. As understood herein “chiral film” refers to a thin layer of material that exhibits chirality.[000108] In one embodiment the invention provides a chiral film comprising: chiral structures comprising at least one metal -coordinated organic complex; andat least one metal linker interspersed within the chiral film.[000109] In one embodiment the metal-coordinated organic complex comprises bipyridine- based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. As understood herein “arms” refer to bipyridine-based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. In one embodiment the unsaturated moieties are selected from: C=C, C=C, C=N, and N=N, or a combination thereof. Not all metal- coordinated organic complex molecules form chiral structures. In one embodiment the metal- coordinated organic complex comprises 3 arms. In one embodiment the metal -coordinated organic complex comprises 6 arms.[000110] As used herein “chiral structures” refers to any assembly of molecules that exhibit chirality. Typically, metal-coordinated organic complex aggregate in solution by pi-pi stacking and form chiral aggregates or assemblies. As used herein the terms “aggregates”, “assemblies” and “structures” are used interchangeably in describing chiral structures that form in solution, and are subsequently deposited on surfaces. When these chiral structures are deposited on a surface, they maintain their chirality under the conditions described herein. As will be shown, metal-coordinated organic complexes that comprise ‘arms’ (for example 3 -arms, or 6-arms) as well as unsaturated moieties (e.g., C=C bonds) within those arms form structures that are chiral in solution, and also result in chiral films comprising those chiral structures.[000111] In one embodiment the chiral structures comprise n- it stacking. The chiral structures comprise TI- it stacking interactions, which arise when the metal -coordinated polypyridyl complexes possess a three-armed or six-armed geometry that promotes planar aromatic overlap. Complexes that do not possess arms exhibit no chirality.[000112] Thus, the molecules that result in chiral structures, and subsequently films, are referred to herein as “chiral molecules”. In some embodiments, the molecules comprising the metal- coordinated organic complexes that have arms (e.g., 3 -arms, 6-arms) and also that have at least a double C=C bond (or other corresponding moieties) in the arms, are chiral. In one embodiment the chiral molecules comprise C=C triple bonds in the arms.[000113] In one embodiment the invention provides chiral films comprising: chiral structures comprising chiral molecules; and at least one metal linker interspersed within the chiral film.[000114] In one embodiment the chiral molecules comprise metal-coordinated organic complexes. In one embodiment the metal-coordinated organic complexes comprise arms and at least C-C double bonds in each arm. In one embodiment the metal -coordinated organic complexes comprise 3 or 6 arms. Another example of chiral molecules that form chiral structurescan be seen in Figure 1 A (Metal-3arm with C=C double bond in the arm) and Figure IB (Metalbarm with C=C double bond in arm).[000115] Figure 40A shows chiral structures in solution comprising Ru, Os, Fe-3-arms complexes as well as Fe-6-arms complex which exhibit chirality in the CD spectra (for 0.6mM solutions in ACN). All of these complexes possess arms and C=C double bonds on those arms, to exhibit chirality in solution. Figure 40B shows UV / visible spectra for chiral structures in solution comprising Ru, Os, Fe-3-arms complexes as well as Fe-6-arms complex.[000116] Figure 41 A compares four solutions with structures comprising complexes where only one (Fe-6-arms with C=C bond in arm) shows a pi-pi stacking effect which is not evident for complexes with no / shorter ligand conjugation (for 0.6mM solutions in ACN). Figure 41B shows the strong absorbance signal for the only chiral structure comprising the Fe-6-arms with C=C bond in arm. Figure 41C shows the decreasing degree of conjugation between various complexes. Only the complex on the left (Fe-6-arms with C=C bond in arm) exhibits chirality in solution when forming chiral structures.[000117] Figure 42A shows a schematic for anion exchange after chiral film formation. Once the chiral film is formed using the chiral anion (TRISPHAT), it is exchanged with a non-chiral anion during electrochemistry cycling. Despite the film losing the chiral anion, the chirality of the film is maintained. Figure 42B shows the results from spectroelectrochemistry for chiral films comprising chiral molecules formed by chiral structures / assemblies. Figures 46A-46B show a decrease in diastereoselectivity with the increase in solvent polarity. Figures 46C-46D show that the for 1(A) - TRISPHAT (A), with concentration variation in DCM, the CD intensity increases with increasing concentration of the complex.[000118] In one embodiment the chiral structures are crystalline. In one embodiment the chiral structures are in a form selected from: sheets, folded sheets, rods, twisted rods, cuboidal, bowties, half bowties, cuboidal, pyramids, or a combination thereof.[000119] In one embodiment the film is electrochromic. In one embodiment the at least one metal-coordinated organic complex is a polypyridyl complex.Chiral Solutions of the invention[000120] In one embodiment the invention provides a chiral solution comprising a solution comprising at least one chiral anion; chiral structures dispersed within the solution; andwherein the chiral structures comprise at least one metal-coordinated organic complex.[000121] In one embodiment the metal-coordinated organic complex comprises bipyridine- based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. In one embodiment the chiral structures comprise pi-pi stacking. In one embodiment the chiral structures are crystalline. In one embodiment the chiral structures are in a form selected from: sheets, folded sheets, rods, twisted rods, cuboidal, bowties, half bowties, cuboidal, pyramids, or a combination thereof. The description of chiral structures are provided throughout the application.[000122] In one embodiment of chiral solution the at least one metal -coordinated organic complex comprises bipyridine-based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. In one embodiment the at least one metal-coordinated organic complex does not comprise bipyridine-based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups. For example, in solution, the presence of the chiral anion does not necessitate the presence of unsaturated moieties such as C=C, C=C, C=N, and N=N; but instead, can comprise C-C single bonds, in various embodiments.[000123] In one embodiment the solution comprises any of the following selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones and diethyl ether or any combination thereof. In one embodiment the solution comprises tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene-l,2-diolato- K2O1,O2)phosphorus(V) [^(ChCeCE)3-)] (= TRISPHAT). In one embodiment the chiral anion comprises TRISPHAT. In one embodiment the chiral anion consists of TRISPHAT.[000124] In one embodiment the invention provides a chiral solution produced by the methods of the invention.Chiral materials of the invention[000125] In some embodiments the invention provides a chiral material comprising structures which comprise of at least one metal -coordinated organic complex. In one embodiment the atleast one metal-coordinated organic complex is a polypyridyl complex. As understood herein, “material” refers to any substance or mixture of substances that constitute matter. Thus, the material can be in solid, liquid or gaseous form. The term “material” can also be understood interchangeably with the terms ‘substance’, ‘matter’, ‘medium’ or the likes. As will be shown, the chiral material primarily comprises molecules.[000126] Metals (e.g., metal salts, metal cations, metal anions, zerovalent metals) used in the invention include those that can work as a metal linker between the substrate and the pyridyl compound or complex material or between two pyridyl compounds or complex materials. In the latter case, the pyridyl complex may be the same or different. Typical metals include, but are not limited to, transition metals, lanthanides, actinides, or main group elements. Transition metals include Zn, Os, Ru, Fe, Pt, Pd, Ni, Ir, Rh, Co, Cu, Re, Tc, Mn, V, Nb, Ta, Hf, Zr, Cr, Mo, W, Ti, Sc, Ag, Au, and Y. Lanthanides include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu. Actinides include Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, or Lr. Main group elements include Zn, Ga, Ge, Al, Cd, In, Sn, Sb, Hg, Tl, or Pb. The metal may be applied as a coordinate metal in either neutral or in an oxidation state. For instance, Pd can be applied as Pd or a Pd(II)-based complex. An example of Pd(II)-based complex is PdC12(PhCN)2. Further, the metals or metal complexes are applied from solution. Suitable solutions can include, but are not limited to, ethers such as tetrahydrofuran and ethyl ether. Metals in the metal- coordinated organic complexes of the invention can be any of the metals described herein above. [000127] As used herein, unless otherwise defined, the term “pyridyl complex” refers to a metal having one or more e.g., two, three, or four pyridyl compounds coordinated therewith.[000128] In various embodiments, the polypyridyl complexes of the invention are represented by Formula I:whereinM is a transition metal selected from Mn, Fe, Co, Ni, Cu, Zn, Ti, C, Cr, Rh, or Ir; n is the formal oxidation state of the transition metal, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai to Ae each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula I via R19R19 each independently is selected from a covalent bond, H2C-CH2, HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2 -COO-, -CONH-, -CON(OH)-, -NR20-, - Si(R2o)2-, an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,5Rxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2o)2, -CON(R2o)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2o)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.[000129] In some embodiments X is a counter ion and may be any suitable anion having a negative charge, e.g., -1 or -2. In various embodiments counterions include, but are not limited to, from (NCh)' and (SC )2'. In one embodiment a dye comprises the counter ion.[000130] Another pyridyl complex used in the invention is an iron-based tris-bipyridyl complex of the general Formula II:wherein n is the formal oxidation state of Fe, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, - CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci- Cio)alkyl, -(C2-Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, - OR20, -COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2O)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or - SO3H;Ai, A3, and A5 each independently is a group of Formula III, z.e., a pyridine or pyridine derivative moiety, or of Formula IV, i.e., pyrimidine or pyrimidine derivative moiety, linked to the ring structure of the complex of general Formula II via R19R19 each independently is selected from a covalent bond, C-C, cis / tran C=C, C=C, N=N, C=N, N=C, C-N, N-C, -COO-, -CONH-, -CON(OH)-, -NR20-, - Si(R2o)2- an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid residues,Rxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, - CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci- Cio)alkyl, -(C2-Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, - OR20, -COR20, -COOR20, -OCOOR20, -OCON(R2o)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2O)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or - SO3H;Bi to B3 each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2-Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, protected carboxyl, or protected amino, wherein the (Ci-Cio)alkyl, (C2-Cw)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, - OR20, -COR20, -COOR20, -OCOOR20, -OCON(R2o)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2O)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or - SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.[000131] X is a counter ion and may be any suitable anion having a negative charge, e.g., -1 or -2. Counterions include, but are not limited to, from (NO,)' and (SC )2'. The value of “m” represents the ratio between the oxidation state of the metal and the valence of the anion. Values of “m” include, but are not limited to, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, or 6. In one embodiment n is theformal oxidation state of Fe, wherein n is 0-3. In one embodiment the counterion is positively charged.[000132] In one embodiment X is a chiral anion. In one embodiment X is a chiral ion. As used herein, “chiral anion” refers to any anionic species that possesses chirality. As understood herein, the chirality of the anions is due to the presence of one or more asymmetric carbon atoms or other chiral centers or a combination thereof within their chemical structures. In some embodiments the chiral structures and films are formed without chiral anions. In various embodiments X is a non-chiral anion. For example, chiral structures and films also form when using a racemic mixture (or a particular ratio of R:S chiral anions). In one embodiments the chiral anion is R. In one embodiment the chiral anion is S. As used herein, “R” and “S” refer to the absolute configuration of chiral centers in molecules, where “R” indicates a clockwise arrangement of substituents and “S” indicates a counterclockwise arrangement.[000133] In one embodiment the chiral anion comprises a mixture of R and S with a ratio of about 1. In one embodiments the chiral anion comprises a mixture of R and S with a ratio of about 1.01. In other embodiments the chiral anion comprises a mixture of R and S with a ratio of between 0.5 to 2. In one embodiments the chiral anion comprises a mixture of R and S with a ratio of between 0.7 to 1.8. In one embodiments the chiral anion comprises a mixture of R and S with a ratio of between 0.9 to 1.5. In one embodiments the chiral anion comprises a mixture of R and S with a ratio of between 0.9 to 1.2.[000134] In one embodiment the chiral anion comprises a mixture of S and R with a ratio of about 1. In one embodiment the chiral anion comprises a mixture of S and R with a ratio of about 1.01. In other embodiments the chiral anion comprises a mixture of S and R with a ratio of between 0.5 to 2. In one embodiment the chiral anion comprises a mixture of S and R with a ratio of between 0.7 to 1.8. In one embodiment the chiral anion comprises a mixture of S and R with a ratio of between 0.9 to 1.5. In one embodiment the chiral anion comprises a mixture of S and R with a ratio of between 0.9 to 1.2.[000135] In one embodiment X is selected from: serinate ([CsFfcNCh]-), alanine ([CsHjNCh]-), tartaric acid ([QHeOe]2-), mandelic acid ([CsFUCh]-), aspartic acid ([C4HeNO4]_), glutamic acid ([C5H8NO4]’), methionine ([CsHnNChS]-), phenylalanine ([CgHnNCh]-), camphorsulfonate ([CIOHI504S]’), isoleucine ([CeHnNCh]-), ibuprofen ([C13H17O2D, leucine ([CeHnNCh]-), naproxen ([CuHnCh]-), valine ([CsHnNCh]-), serine ([CsFFNCh]-), cysteine ([CsFFNChS]-), naproxenate ([CUHBOS]-), proline ([CsFfcNCh]-), histidine ([CeFfcNsCh]-), tyrosine ([CgHiiNCh]-), glutamate ([CsFUNCU]-), tryptophan ([C11H12N2O2D, threonine ([QFbNCh]-), L-Tartrate ([C4H40e]2'), D-Tartrate ([C4H40e]2'), phenylalaninate ([CgHwNCh]-), ibuprofenate([C13H17O2]-), L-Malate ([C-iEUCh]2'), D-Malate ([C4H4O5]2'), lactate ([C3H5O3D, D-Lactate ([C3H5O3D, mandelate ([CsHjCh]-), leucinate ([CeH^NCh]-), aspartate ([C4H5NO4]-), phenylglycinate ([CsHsNCh]-), camphorate ([C10H15O4D, camphanate ([C10H15O4D, methioninate ([CsHnNChS]-), norbomane-2-carboxylate ([C7H11O2D, troponate ([C7H11O2D, cysteinate ([CsHeNChS]-), alaninate ([CsFFNCh]-), isoleucinate ([CeHnNCh]-), valinate ([C5H11NO2D, and tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene-l,2-diolato- K2O1,O2)phosphorus(V) [(PCChCeCU)3-)] (= TRISPHAT), or any combination thereof.[000136] In one embodiment the chiral anion comprises a negatively charged functional group. In one embodiment the negatively charged functional group is selected from: phosphates (PO43), sulfonates (RS(=0)2.0 ), sulphates (SCh)2', carboxylates (RCOO-), and borates (I^B"), or a combination thereof.[000137] In one embodiment the chiral anion comprises the deprotonated form of any of the following selected from: tartaric acid, mandelic acid, amino acids, lactic acid, camphor, sulfonic acid, or a combination thereof. In one embodiment the chiral anion comprises any of the following selected from: chromophore, fluorophore, metal, boron-dipyrromethene (BODIPY), porphyrin, fluorene, azobenzene, stilbene, rhodamine, indocyanine, polycyclic aromatic hydrocarbons, at least one halide, electron withdrawing group, electron donating group, or a combination thereof. In one embodiment the anion is selected from: sulforhodamine SR 101, azo compounds, methyl orange, methylene blue, ^-carotene, and retinal, or a combination thereof.[000138] In one embodiment the electron withdrawing group is selected from: fluorocarbons, aldehydes, halogens, carbonyl, cyanides, nitro, sulfonic acid, carboxylic acid, ester group, amide group, and nitroso group, or a combination thereof. In one embodiment the electron donating group is selected from: alkyl, allyl, vinyl, phenyl, alkylamino, alkoxy, amino, hydroxyl, thiol, and ether, or a combination thereof. In one embodiment the polycyclic aromatic hydrocarbons are selected from: naphthalene, biphenyl, fluorene, anthracene, phenanthrene, phenalene, tetracene, chrysene, triphenylene, pyrene, pentacene, perylene, benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene, and benzo[c]fluorene or a combination thereof.[000139] In one embodiment the polypyridyl complex is represented by Formula II:wherein n is the formal oxidation state of Fe, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai, A3, and A5 each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula II via R19III IVR19 each independently is selected from a covalent bond, H2C-CH2, cis / trans HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2 -COO-, -CONH-, -CON(OH)-, -NR20-, -Si(R2o)2- an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid•W "N- vresidues, orRxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Bi to B3 each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, - N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl[000140] In one embodiment the chiral material forms structures. In turn, those structures are chiral. In one embodiment the chiral material forms structures with a size ranging between 10 nm to 100 pm. In one embodiment the chiral material forms structures with a size ranging between 10 nm to 10 pm. In one embodiment the chiral material forms structures with a size ranging between 100 nm to 10 pm. In one embodiment the chiral material forms structures with a size ranging between 1 pm to 10 pm. As understood herein the “size” refers to the length of at least one of the dimensions of a structure. For example, the length, width, and / or height of that structure. Examples of chiral structures include, but are not limited to: film, nanoparticle, crystal, wire, rods, spheres, quantum dot, tube, etc. Examples of crystal forms include, but are not limited to: polycrystalline, single crystal, amorphous, quasicrystal, nanocrystalline, liquid crystal, etc.[000141] In one embodiment the invention provides a film comprising the chiral material of the invention. In one embodiment the film comprises at least one chiral material of the invention.[000142] The chiral materials of the invention can also be provided in liquid form generally referred to as a “chiral solution”. Various examples and embodiments of which are delineated herein. In one embodiment the chiral material comprises a solvent, resin, or gel, thereby producing a chiral solution. In one embodiment the solvent is selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile,tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones and diethyl ether, or any combination thereof.[000143] In one embodiment the resin comprises any of the following selected from: acrylic resin, alkyd resin, epoxy resin, polyurethane resin, vinyl resin, phenolic resin, silicon resin, UV- curable resin, or a combination thereof.Methods of the Invention[000144] As used herein, the term “chiral solution” is any solution that exhibits chiral behavior. In various embodiments the chiral solution is a dispersion, suspension, or emulsion. A chiral dispersion is any solution wherein chiral structures are dispersed within a liquid. There are two primary methods of forming chiral solutions. One method involves using a chiral seed to affect the chirality of an initially racemic mixture, and another method involves disposing chiral anions in a solution to direct the chirality of the solution.[000145] In one embodiment the invention provides a method of producing a chiral solution, the method comprising: providing a solvent; disposing at least one metal-coordinated organic complex in the solvent, producing an approximately racemic solution; providing a chiral seed comprising a metal-coordinated organic complex; and disposing the chiral seed into the racemic solution thereby producing the chiral solution comprising chiral structures formed from the at least one metal- coordinated organic complex.[000146] The metal-coordinated organic complex of the step of disposing the at least one metal- coordinated organic complex in the solvent can be the same metal -coordinated organic complex comprised within the chiral seed, or otherwise, it can be a different metal -coordinated organic complex. As used herein the term “chiral seed” refers to a substance introduced into a solution to act as a nucleation site to at least partially determine the outcome configuration of the chirality of the chiral solution. As disclosed herein, the form of the chiral seed is not limited. For example, it can be a nanostructure, nanoparticle, aggregate, crystal, etc.[000147] In one embodiment the solvent is selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycolethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2- pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones, and diethyl ether or any combination thereof.[000148] In one embodiment the racemic solution has a concentration ranging between 0.1 to 10 mM. In one embodiment the racemic solution has a concentration ranging between 0.1 to 5 mM. In one embodiment the racemic solution has a concentration ranging between 0.1 to 2 mM. In one embodiment the racemic solution has a concentration ranging between 0.1 to 1 mM. In one embodiment the racemic solution has a concentration ranging between Ito 2 mM. In one embodiment the racemic solution has a concentration of about 1 mM.[000149] In one embodiment the chiral seed is selected from: right-handed chiral seed to produce a right-handed chiral solution; or left-handed chiral seed to produce a left-handed chiral solution.[000150] In one embodiment the chiral seed is in the form of an aggregate, nanoparticle, crystal, flake, film or a combination thereof. The crystal can be amorphous, polycrystalline, or single crystal. In one embodiment the chiral seed has a size ranging between 10 nm to 10 pm. In one embodiment the chiral seed has a size ranging between 10 nm to 1 pm. In one embodiment the chiral seed has a size ranging between 10 nm to 500 nm. In one embodiment the chiral seed has a size ranging between 10 nm to 100 nm.[000151] In one embodiment the invention provides a method of producing a chiral solution, the method comprising: providing a solution comprising at least one chiral anion; disposing at least one metal-coordinated organic complex in the solution thereby producing a chiral solution comprising chiral structures of the at least one metal-coordinated organic complex.[000152] In one embodiment the invention provides a method of producing a chiral film, the method comprising: a) providing a substrate; b) depositing a linker layer; c) depositing a chiral solution as disclosed herein; andd) repeating steps (b) and (c) until a desired thickness is reached, forming a chiral film.[000153] In one embodiment the invention provides a method of producing a chiral film, the method comprising: a) providing a substrate; b) depositing a linker layer comprising at least one metal linker; c) depositing a chiral solution comprising chiral structures and a chiral anion, wherein the chiral structures comprise at least one metal-coordinated organic complex; and d) repeating steps (b) and (c) until a desired thickness is reached, forming a chiral film.[000154] In one embodiment the invention provides a method of producing an electrochromic chiral film, the method comprising: a) providing a substrate; b) depositing a linker layer comprising at least one metal linker; c) depositing a chiral solution comprising chiral structures and a chiral anion, wherein the chiral structures comprise at least one metal-coordinated organic complex; and d) repeating steps (b) and (c) until a desired thickness is reached, forming a chiral film.[000155] In one embodiment the method further comprises at least partly removing the chiral anion by exchange with achiral counterions, and wherein the electrochromic chiral film remains chiral. Thus, it is observed that the electrochromic chiral film retains its chiroptical properties even after partial or complete exchange of the chiral anion with achiral counterions. This indicates that the chirality of the film arises not from the presence of the chiral anion but is at least partly embedded in the chiral architecture of the metal-coordinated organic complexes themselves, and their corresponding chiral structures / assemblies in solution. During the deposition process, these chiral structures / assemblies are thought to self-assemble or orient in a manner that preserves their stereochemical configuration, leading to a chiral configuration within the film. Once incorporated into the film, the chiral structures at least partially maintain their spatial arrangement, possibly stabilized by coordination geometry, n- it interactions, or hydrogen bonding, such that the film exhibits chirality independent of the original chiral counterion.[000156] In one embodiment the achiral counterions comprise any of the following selected from: PFe", organic anions, pseudohalides, boron -based anions, hydride-based anions, halideanions, phosphorus-based fluoroanions, oxyanions, and oxide-based anions, or a combination thereof. Other examples of achiral counterions include, but are not limited to: Dichromate (C O?2), Sulfide (S2), Tetrafluoroborate (BF4 ), Tri fluorob orate (BF3 ), Fluoride (F ), Bicarbonate (HCCf ), Hexafluorophosphate (PFe ), Cyanide (CN"), Nitrite (NO2 ), Phosphide (P3), Tetraphenylborate (BPtu ), Chromate (CrOF ), Acetate (CH3COO ), Iodide (I ), Oxide (O2), Thiocyanate (SCN"), Dihydrogen phosphate (H2PO4 ), Tetrakis(pentafluorophenyl)borate (BfGFsfi ), Perchlorate (CIO4 ), Hydroxide (OH ), Borohydride (BH4 ), Permanganate (MnCf ), Nitrate (NO3 ), Bromide (Br ), Phosphate (PO43), Nitride (N3), Hydrogen phosphate (HPO42), Carbonate (CO32), Sulfate (SO42), Perborate (BCf ), Peroxide (O22), Chloride (CF), Hypophosphite (H2PO2 ), Hydride (H ), etc.[000157] In one embodiment the invention provides a chiral solution produced by any of the methods of the present invention.[000158] In one embodiment the substrate comprises any of the following selected from: glass, doped glass, metal-oxide, indium tin oxide (ITO)-coated glass, fluorine-doped tin oxide (FTO)- coated class, silicon, doped silicon, zinc oxide (ZnO), Si(100), Si( 111), SiCh, SiH, silicon carbide mirror, quartz, metal, metal oxide, mixture of metal and metal oxide, group IV elements, mica, carbon-based materials, graphene, carbon nanotubes, graphite comprising intercalated metal cations, polymer, plastic, zeolite, clay, membrane, optical fiber, ceramic, metalized ceramic, alumina, electrically-conductive material, semiconductor, steel, and stainless steel, gold, silver, platinum, copper, zinc, aluminum or any combination thereof. In one embodiment the substrate comprises: glass, doped glass, metal-oxide, indium tin oxide (ITO)-coated glass, fluorine-doped tin oxide (FTO)-coated class, silicon, doped silicon or zinc oxide (ZnO). In one embodiment the substrate is flexible.[000159] In some embodiments the substrate further comprises a conductive polymer. Examples of conductive polymers include, but are not limited to: polyaniline (PANI), polyacetylene (PA), polythiophene, polyphenylene vinylene (PPV), poly(3,4-ethylenedi oxythiophene) (PEDOT), polypyrrole (Ppy), polyfluorene, poly(3 -hexylthiophene) (P3HT), poly(phenylene sulfide) (PPS), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), or combinations thereof, etc.[000160] In one embodiment the depositing is selected from: spin coating, dip coating, brush coating, roller coating, flow coating, drop casting, mill rod coating, chemical vapor phase deposition (CVD), roll-to-roll (R2R) processing, electropolymerization, printing, layer-by-layer deposition, organic powder coating, inkjet printing, spray coating, ultrasonic spray coating, blade-coating, physical vapor deposition (PVD), Meyer bar coating, or a combination thereof.[000161] In one embodiment the linker comprises a metal salt. In one embodiment the metal salt is a metal-based coordination complex.[000162] In one embodiment the linker has the general formula MXYL1L2; wherein M is metal;X is a halide counterion;Y is a halide counterion; andLi = L2 or Li ± L2;Li and L2 are one ligand with two binding groups wherein each binding group is the same or different.[000163] In one embodiment the M is: zerovalent, monovalent, bivalent or trivalent. In one embodiment M is selected from: Fe, Co, Zn, Ni, Pt and Pd. In one embodiment the linker is selected from: PdCh, PdChCCFhCbTh, PdCh(PhCN)2, PdCbfCxHn) where CxHn is cycloocta- 1,5-diene (cod) or abbreviated PdCh(cod), PdSO4, Pd(NO3)2, Pd(OAc)2, PdBr2, Pd(OSO2CF3)2, Pd(BF4)2,PtCl2, PdC12(Sme2)2, PdBr2, PdBr2(CH3CN)2, PdBr2(PhCN)2, PdBr2(C8Hi2) where C8Hi2 is cycloocta-l,5-diene (cod) or abbreviated PdBr2(cod), PdSO4, Pd(NO3)2, Pd(OAc)2, PdBr2, Pd(OSO2CF3)2, Pd(BF4)2, PdC12(olefm)nwith n = 1, 2 or 3, PdBr2(olefm)nwith n = 1, 2 or 3, PtC12(olefm)nwith n = 1, 2 or 3, PtBr2(olefm)nwith n = 1, 2 or 3, PtChPtC^CFhCbTh, PtC12(PhCN)2, PtCl2(C8Hi2) where C8Hi2 is cycloocta-l,5-diene (cod) or abbreviated PtC12(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtCl2, PtBr2(CH3CN)2, PtBr2(PhCN)2, PtBr2(C8Hi2) where C8HI2is cycloocta-l,5-diene (cod) or abbreviated PtBr2(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtBn, Pt(OSO2CF3)2, Pt(BF4)2, PtC12(Sme2)2, PtBr2(Sme2)2, CuSO4, CuCl2, Cu(OH)2, Cu(NO3)2, Cu(Oac)2, CuBr2, Cu(OSO2CF3)2, Cu(BF4)2, Cu(C6H5CO2)2, NiCh, NiC12(CH3CN)2, NiCh(PhCN)2, NiC12(C8Hi2) where C8Hi2 is cycloocta-l,5-diene (cod) or abbreviated NiCl2(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2, Ni(BF4)2,NiCl2, NiCl2(Sme2)2, NiBr2(CH3CN)2, NiBr2(PhCN)2, NiBr2(C8Hi2) where C8Hi2 is cycloocta-l,5-diene (cod) or abbreviated NiBr2(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2, Ni(BF4)2, NiBr2(Sme2)2, NiC12(olefm)nwith n = 1, 2 or 3, NiBr2(olefm)nwith n = 1, 2 or 3, ZnCb, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBn, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBr2(olefm)nwith n = 1, 2 or 3, ZnCl2(olefin)n with n = 1, 2 or 3, K2PdCl4, K2PdCl6, Na2PdCl4, Na2PdCl6, K2PtCl4, K2PtCl6, Na2PtCl4, Na2PtCle, FeCh, FeBr2, Fe(NO.3)2, FeSO4, FeBr2(olefm)nwith n = 1, 2 or 3, FeC12(olefm)nwith n = 1, 2 or 3, Fe(OAc)2 or any combination thereof.[000164] In one embodiment the metal -base of the metal-coordinated organic complex is selected from: Os, Fe, Ru, Mn, Cu, Zn, Ni, Cr, Ti, V, Ir, or Rh.[000165] In one embodiment the method further comprises cleaning and drying the chiral film after at least one step. Examples of cleaning include but are not limited to: washing in organic solvents, sonication cleaning, immersion in solvents, UV-ozone cleaning, plasma etching, drying under a stream of gas, heating and vacuum drying or any combination thereof. Examples of organic solvents used for washing include, but are not limited to: acetonitrile (ACN), tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), hexane and diethyl ether or any combination thereof.[000166] The chiral materials of the present invention can be used for electro-optic devices. The chiral nature of a film, for example, can be used as an additional degree of freedom for the purposes of barcoding and QR-coding. In one example, an array of red dots can be printed, but only a particular pattern of dots displaying chirality can be used, which are detected by a specialized detector. This has security-related applications such as counterfeiting prevention and verification. In some applications the printed pattern can additionally exhibit electrochromism. Thus, the device can exhibit localized electrochromism and chirality, separately or at the same time, depending on the conditions. In some embodiments the film-form of the chiral material is colorless. In other embodiments the film-form of the chiral material has color.[000167] In some embodiment the drying is selected from: drying under a stream of gas, annealing, heating and vacuum drying, or any combination thereof.[000168] In one application, the chiral materials can be patterned in a pixelated array, each pixel having a particular optical property e.g., a color and / or a chirality having a value of 0, -, or +. Examples of such pixelation for security printing are shown in Figures 39A-39C. In various embodiments, the intensity of the colors can be varied by the conditions of the deposition. The amount of data stored in an array of such pixels will be large (without even using the electrochromic properties). If one applies a potential, the information that can be stored in a small array of pixels will be even large. In one embodiment the array of pixels is at least 2 x 2. The pixelation can also be patterned into a desirable pattern. For the purposes of security printing, this can include a particular image, shape, or logo, for example. Figure 39A shows an array of pixels for the application of security printing with and without the need for electrochromic properties. Each pixel represents a different metal-organic complex (i.e., based on a different metal center) and / or a different chiral element. With twenty four color options per row and four rows, this provides a total of 244pixel configurations. Figure 39B shows a similar array to Figure39A but with the additional option of using light and dark variations of specific colors e.g. light / dark purple. This increases the number of pixelation configurations considerable, to the order of about 616. Figure 39C shows another security printing application but with selective addressing of colors. The intensity of the optical signals related to chirality will change as well and can be read out.Devices comprising chiral films[000169] Multilayered EC materials (and chiral films) have unique electrical properties suitable in applications such as smart windows, electrochromic windows, smart mirrors, optical filters, frequency doubling devices, spatial light modulators, pulse shapers, displays, signs, plastic electronics, lenses, sensors, to name a few.[000170] Devices comprising the chiral films of the invention are now disclosed. As stated elsewhere herein, the chiral films can also have an electrochromic function. The invention provides a device comprising: a substrate; a chiral layer comprising the chiral material of claim 1, the chiral layer being disposed on the substrate; an electrolyte disposed on the chiral layer; an ion storage layer disposed on the electrolyte; and a counter electrode in contact with the ion storage layer.[000171] The device can be used as an electrochromic device, an energy storage device, a capacitor, supercapacitor, hybrid capacitor, and the likes.[000172] In one embodiment the electrolyte is selected from: ACN / PC / PMMA / trifluoromethylsulfonamide lithium salt, polymethyl methacrylate (PMMA), propylene carbonate (PC), LiCFsSCh, LiBF4, Li2+2xZni-xGeO4 (LiSICON), glassy lithium phosphorus oxynitride (LIPON), and LiCICh or any combination thereof. In one embodiment the ion storage layer comprises any of the following selected from: polymers, copolymers, metalorganic polymer, coordination polymer, molecular film, metallic coating, transparent conducting oxides, metal oxides, metal fluorides, metal nitrides, metal sulfides, nanocrystalline metal oxides, mixed metals oxides, redox-active species, carbon-based materials, graphene-based materials, buckminsterfullerenes, nanotubes, 2D materials, biomolecules, nanowires, polymethyl methacrylate (PMMA), benzocyclobutene (BCB) based polymers, poly(3,4- ethylenedioxythiophene), poly(styrenesulfonate), conjugated dithiolenes, polyelectrolytes, organic salts, inorganic salts, quinone-based compounds, viologen-based compounds, antimony-doped tin oxide (ATO), pyridine blue (PB), polyaniline, polypyrrole, lithium cobalt oxide, lithium cobalt oxide, indium tin oxide, fluorine doped tin oxide, niobium oxide, molybdenum oxide, zinc oxides, aluminum oxide, nickel oxides, ceric oxide, metal doped nickel oxides, lithium doped nickel oxides, lithium doped titanium oxides, polymetal oxides, nanoparticles, metallic nanoparticles, nickel hexacyanoferrate, iron hexacyanoferrate, lithium hexacyanoferrate, sodium hexacyanoferrate, manganese hexacyanomanganate, halogen-doped metal oxides, lithium sulfide, lithium garnet, lithium phosphorous oxynitride, lithium manganese oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, sodium nickel chloride and activated carbon.[000173] In one embodiment the counter electrode comprises any of the following selected from: glass, doped glass, metal-oxide, indium tin oxide (ITO)-coated glass, fluorine-doped tin oxide (FTO)-coated class, silicon, doped silicon, zinc oxide (ZnO), Si(100), Si(l l l), SiCh, SiH, silicon carbide mirror, quartz, metal, metal oxide, mixture of metal and metal oxide, group IV elements, mica, graphite comprising intercalated metal cations, polymer, plastic, zeolite, clay, membrane, optical fiber, ceramic, metalized ceramic, alumina, electrically-conductive material, semiconductor, steel, and stainless steel, gold, silver, platinum, copper, zinc, aluminium or any combination thereof.[000174] In one embodiment the chiral layer is in the form of an array of pixels and / or patterned on the substrate. As shown in Figures 39A-39C an array of pixels can be used in any variety of combinations to form unique authentication codes, that operate under a variety of stimuli e.g., an applied bias. In one embodiment the device further comprises a lamination. Otherwise, the device can be entirely encapsulated by a housing or any form of encapsulation material.[000175] In one embodiment the chiral layer is electrochromic.[000176] In one embodiment the invention provides an electro-optical system comprising: the device of the invention; at least one sensor configured to detect an optical state; a power supply; and a controller configured to control the optical state of the device by means of an applied potential; wherein the controller and the power supply are configured to apply a bias potential across the chiral layer thereby inducing at least one change in the optical state of the chiral layer and wherein the at least one sensor is configured to communicate the optical state to the controller.[000177] As such, the system can comprise one or more devices of the invention. In various embodiments the system is modular, comprising more than one of the devices of the invention. As understood herein, and in various embodiments, the devices (and their corresponding systems) that comprise a chiral component may not always be chiral, but depend on the conditions under which they are subjected.[000178] In one embodiment the device is configured such that the device is in a bleached state when a bias potential is applied. In one embodiment the at least one sensor is an electro-optic sensor. Examples of sensors include, but are not limited to: photodetector, photodiode, phototransistor, photomultiplier tube (PMT), spectrophotometer, reflectance spectrometer, transmittance spectrometer, colorimeter, color sensor, UV-vis spectrophotometer, UV sensor, infrared sensor, image sensor, complementary metal-oxide semiconductor (CCD) sensor, charge- coupled device (CCD) sensor, polarimeter, photoluminescence sensor, fluorescence sensor, optical sensor, ammeter, voltmeter, ohmmeter, multimeter, potentiometer, galvanometer, magnetometer, hall effect monitor and light dependent resistor (LDR), or a combination thereof. [000179] In one embodiment the optical state is selected from: color, chirality, intensity, polarization, phase, reflectivity, and luminescence.[000180] In one embodiment the invention provides a security authentication system comprising the electro-optical systems of the invention. Examples of security authentication includes, but is not limited to: QR codes, barcodes, biometric authentication, smart cards, wearable electronics, smart cards, one-time passwords, RFID / NFC tags, contactless cards, currency, coinage, paper money, secure tokens, product identification, etc.[000181] In various embodiments, the devices of the invention are used in any of the following selected from: smart windows, electrochromic windows, smart mirrors, optical filters, frequency doubling devices, spatial light modulators, pulse shapers, displays, signs, plastic electronics, lenses, and sensors. In various embodiments, the electro-optical systems of the invention are used in any of the following selected from: smart windows, electrochromic windows, smart mirrors, optical filters, frequency doubling devices, spatial light modulators, pulse shapers, displays, signs, plastic electronics, lenses, and sensors.EXAMPLESEXAMPLE 1 Methods[000182] UV / Vis Spectroscopy. UV / Vis spectra were recorded on a Cary 100 spectrophotometer. The absorbance was measured using the Cary Win UV-Scan application program, version 3.00 (182) by Varian (200-800 nm), while the transmittance was measured using the Cary Win UV-Kinetics application program, version 3.00 (182) by Varian. Bare substrates were used to compensate for the background absorption.[000183] X-ray Photoelectron Spectroscopy. XPS measurements were carried out on FTO / glass substrates (2.0 cm x 2.0 cm) with a Kratos AXIS ULTRA system, using a monochromatic Al Ka X-ray source (hu = 1486.6 eV) at 75 W and detection pass energies ranging between 20 and 80 eV. Curve fitting analysis was based on Shirley or linear background subtraction and application of Gaussian-Lorenzian line shapes.[000184] Circular Dichroism Measurements. All measurements were carried out using Applied Photophysics Chirascan instrument, using Pro-Data Chirascan software, version 4.5.1840.0. All measurements were carried out in a 1 mm cuvette, at room temperature, unless otherwise is mentioned, at wavelength range of 350-750 nm, with step size of 1 nm and bandwidth of 1.2 nm. The resolution was set to be 1 s per data point.[000185] Scanning electron microscopy (SEM) measurements. SEM measurements were performed using HRSEM ULTRA-55 ZEISS and HRSEM SUPRA-55 VP ZEISS instruments at an EHT voltage of 1.5 kV. Images were collected in secondary and backscattered electron modes by using Everhart- Thornley and energy selective backscattered detectors, respectively. SEM samples were prepared by placing a drop of 0.6 mM solution of complexes 1-4, on a silicon substrate and air drying it.[000186] Transmission electron microscopy (TEM) and scanning transmission electron microscopy (S-TEM) measurements. TEM samples were prepared by drop cast preparation of nanostructures onto carbon support film.[000187] TEM tilt series for tomographic reconstruction were recorded in a FEI T12 microscope operated at 120 kV acceleration voltage. Images were recorded during a continuous fast tilt of the sample holder around a single axis over a tilt range of 120°. The tilt sequence took 34 s during which images were recorded with a Gatan One View camera operating in stack acquisition mode with a fix frame time 159 ms, corresponding to a tilt increment of 0.56° per frame. During tilt rotation specimen displacements and defocus were electronically compensated. Tomogramswere reconstructed after iterative feedback refinement of image alignment using a SIRT algorithm.[000188] STEM images were recorded at an accelerating voltage of 200 kV in a FEI Tecnai F20 Twin microscope. STEM images were taken on a Gatan 807 BF / ADF detector. For nanodiffraction an electron microprobe with a semi -convergence angle of 0.4 mrad, corresponding to a FWHM of 3 nm, was rastered over a region of interest. Nanodiffraction raster data sets were taken using a custom DigiScan script on an Orius 600 A CCD camera in a Gatan Quantum 967 GIF.[000189] Cryo-TEM measurements. Cryogenic transmission electron microscopy (cryo- TEM) imaging was performed on a Thermo-Fisher Talos F200C, FEG-equipped high resolution- TEM, operated at 200 kV. Specimens were transferred into a Gatan 626DH cryo-holder and equilibrated below -170 °C. Micrographs were recorded by a Thermo-Fisher Falcon III direct detector camera, at a 4k * 4k resolution. Specimens were examined using a low-dose imaging procedure to minimize electron-beam radiation damage and were acquired on average at a dose of less than 7 e / A2. Images were acquired using the TEM Imaging and Acquisition (TIA) software.[000190] Cryo-TEM specimens were prepared in a controlled environment vitrification system (CEVS). Since the sample is composed of a suspension in dichloromethane (DCM) and methanol at a 1 : 1 ratio, the CEVS air was saturated with a solution of the same solvent ratio. A drop of the solution was placed on a carbon-coated perforated polymer film, supported on a 200 mesh TEM grid, mounted on tweezers. The drop was turned into a thin film (preferably less than 300 nm) by blotting away excess solution with a metal strip covered with a filter paper. The grid was then plunged quickly into liquid nitrogen at its boiling point (-196 °C). Although liquid nitrogen is a poor cryogen (compared to liquid ethane at its freezing point), regions in the specimens were found which were properly vitrified. Liquid ethane could not be used for the vitrification of this sample because it would have dissolved the organic solvent. All the specimens were quenched from 25 °C.[000191] Atomic Force Microscopy. AFM images were recorded using a Solver P4710 (NT- MDT, Russia) Microscope, or JPK AFM (JPK Nanowizard III, Berlin, Germany), operating in AC mode or semi-contact scanning mode, with -100 pm silicon cantilevers having a resonant frequency of 70-90 kHz. The roughness values, Rrms, were obtained from 500 nm x 500 nm images, using Nova 1.0.26 RC1 software.[000192] Focused Ion Beam Microscopy. SEM images were recorded using Helios 600 FIB / SEM Dual Beam Micro-scope (FEI), operating at 5 keV. The images were taken at thesurface of the samples, and at cross-sections that were milled by a 30 keV Ga+focused ion beam (FIB). The sample was first locally coated with a 150-200 nm thick layer of Pt using electronbeam assisted deposition, which was followed by an ion-beam assisted deposition of a 500-600 nm thick layer of Pt. The Pt coating protects the MA layer from ion beam damage providing a clean edge of the cross section.[000193] Computational calculations. Geometries were optimized using ORCA 4.0.1 using Grimme’s B97-3c method, which is a low-cost variant of the Becke97-D (B97-D) functional including Grimme’s third-generation empirical dispersion correction with Becke-Johnson dampening (denoted D3BJ) and Grimme’s geometrical counterpoise correction (gCP). Energies were then also calculated using Gausian 16 Revision B.01 using Truhlar’s local version of the Minnesota-15 functional family (i.e., MN15-L) with an empirical dispersion (D3-version) with parameters taken from Goerigk et al. With this functional the second revision (def2) of Ahlrichs and coworkers’ basis sets (def2-SVP) was used. When using a GGA functional, density fitting basis sets, specifically Weigend and coworkers W06 fitting basis set, were used to speed up the calculations.[000194] Dynamic Light Scattering (DLS) measurements. All measurements were carried out using Malvern Zetasizer NANO instrument, with Zetasizer software, version 7.10. All measurements were carried out in a 1 cm cuvette, at room temperature.[000195] Electrochemical Characterization. Electrochemical experiments were carried out using a CHI660A or CHI760E electrochemical workstation. The following configuration of the electrochemical cell was used: FTO-coated glass or ITO-coated PET substrates (size of 2 cm * 2 cm, 4 cm x 4 cm, 2 cm x 6 cm, 3 cm x 6 cm or 6 cm x 6 cm) served as the working electrode, Ag / Ag+was used as the reference electrode, and a Pt wire as the counter electrode. Tetrabutylammonium hexafluorophosphate (TBAPFe) in ACN (0.1 M) was used as the supporting electrolyte. The electrochemical measurements of the devices were carried out with FTO-coated glass or ITO-coated PET substrates (2 cm x 2 cm, 4 cm x 4 cm, 6 cm x 2 cm or 6 cm x 6 cm) serving as the working electrode, and a corresponding bare substrate as the reference and the counter electrodes.[000196] Crystallization of Complexes 1, 2 or 2’. Single crystals of complexes 1, 2 or 2’ suitable for X-ray analysis were obtained at room temperature, upon slow evaporation of a 2 mL CEECh MeOH (1 : 1 v / v) solution containing ~1 mg of the complex.[000197] X-ray Crystal Structure Analysis of Complex 1. Crystal data: Cs4H45FeN9 + 2(PFe), purple plate, 0.30 x 0.2 x 0.01 mm3, triclinic, space group P-1, a = 15.2797(11) A, b = 21.3748(15) A, c = 21.7718(15) A, a = 74.223(10)°, p = 77.054(10)°, y = 79.381(11)° from 3462reflections, T = 100(2) K, V = 6610.9(9) A3, Z = 4, Fw = 1165.78, De = 1.171 Mg m'3, p = 0.348 mm'1. Data collection and processing: Rigaku XtaLab diffractometer, Pilatus 200K detector, MicroMax003 MoKa (X = 0.71073 A), -15 < h < 15, -21 < k < 21, -21 < 1 < 21, frame scan width = 0.50°, scan speed 1.0° per 80 s., typical peak mosaicity 0.70°, 55317 reflections collected, 13716 independent reflections (Rint = 0.1349). The data were processed with Rigaku Crys-AlisPro. Solution and refinement: Structure solved with SHELXT-2013. Full matrix leastsquares refinement based on F2with SHELXL-2013 on 1546 parameters with 208 restrains gave final R1 = 0.0776 (based on F2) for data with I > 2o (I), and R1 = 0.1296 on 13716 reflections. Goodness of fit on F2= 0.937, largest electron density peak = 1.291 e A'3, largest hole = -0.314 e- A'3. The crystallographic data has been deposited with the CCDC 1474722.[000198] X-ray Crystal Structure Analysis of Complex 2. Crystal data: C?2H54FeNi2 + 2(PFe), black prism, 0.1 x 0.09 x 0.01 mm3, monoclinic, space group P2(l) / c, a = 10.6945(7) A, b = 24.877(2) A, c = 26.8986(17) A, p = 106.314(5)° from 4302 reflections, T = 100(2) K, V = 6868.2(9) A3 , Z = 4, Fw = 1435.06, De = 1.388 Mg m'3, p = 2.935 mm'1. Data collection and processing: Rigaku XtaLab diffractometer, Pilatus 200K detector, MicroMax003 MoKa (X = 1.54184 A), graphite monochromator, -11 < h < 11, -26 < k <2 3, -28 < 1 < 20, frame scan width = 0.50°, scan speed 1.0° per 60 s., typical peak mosaicity 0.70°, 34647 reflections collected, 8360 independent reflections (Rint = 0.0984). The data were processed with Rigaku CrystalClear. Solution and refinement: Structure solved with SHELXT-2013. Full matrix least-squares refinement based on F2with SHELXL-2013 on 940 parameters with 98 restrains gave final R1 = 0.1360 (based on F2) for data with I > 2o (I), and Ri = 0.1569 on 8360 reflections. Goodness of fit on F2= 1.050, largest electron density peak = 1.255 e A'3, largest hole = -0.698 e A'3, CCDC 1474723.[000199] X-ray Crystal Structure Analysis of Complex 2’:[000200] Crystal data: C?2H66FeNi2+ 2(PFe), red-orange plate, 0.12 x 0.06 x 0.002 mm3, triclinic P-1, a=l l.3731(7) A, b=18.9055(12) A, c=20.1189(12) A, a=107.045(6)° , P=96.303(5)°, y=106.948(6)° from 29437 reflections, T=100(2)K, V=3865.0(4) A3, Z=2, Fw=1445.15, Dc=1.242 Mg.m'3, p=2.604 mm~l. ata collection and processing: Rigaku XtaLab diffractometer, Pilatus 200K detector, MicroMax003 CuKa ( = 1.54184 A), Max -Flux optics - 10<h<10, -18<k<l 8, -19<1<19, frame scan width = 0.50°, scan speed 1.0° per 120 sec, typical peak mosaicity 0.6°, 29437 reflections collected, 7212 independent reflections (R-int =0.0666). The data were processed with Rigaku CrysAlisPro. Solution and refinement: Structure solved with SHELXT-2016. Full matrix least-squares refinement based on F2with SHELXL-2016 on 931 parameters with 381 restraints gave final Ri= 0.1019 (based on F2) for data with I>2c(I) and,Ri= 0.1278 on 7212 reflections, goodness-of-fit on F2= 1.238, largest electron density peak 0.585 e.A'3Largest hole -0.334 e.A'3. SQUEEZE was used; disordered waters in channel could be seen but not refined.[000201] Formation of Unimolecular Molecular Assemblies by Spin Coating. MAI-4 were obtained by iterative spin-coating of the solutions of PdCh(PhCN)2 and of complexes 1-4. A THF solution of PdC12(PhCN)2 (3.0 mM) was used for the formation of MAI-2 and MA4. For the formation of MA3, a THF solution of PdCh(PhCN)2 (4.0 mM) was used. CHzCb MeOH (1 : 1 v / v) solutions of complexes 1-4 (0.6 mM) were used for their deposition. The PdC12(PhCN)2 solution was dropcasted on FTO / glass or ITO / PET substrates (2 cm - 2 cm, 4 cm / 4 cm or 6 cm x 6 cm). Subsequently, the substrate was spun at 500 rpm for 10 s and then at 1000 rpm for 30 s. Next, a solution of the corresponding complex 1-4 was dropcasted after 80 s on the substrates, which was spun as above. The substrates were then immersed in acetone for 30 s, and were dried under a gentle stream of air. The PdC12(PhCN)2 deposition and subsequent complex (1-4) deposition step is referred to as a single deposition cycle. For the formation of MAI, MA2 or MA4, the deposition cycle was repeated 18 times. For the formation of MA3, the deposition cycle was repeated 12 times. The deposition of the first layer of PdCh was found to be necessary for binding of the metal complexes 1-4 to the substrate surface.[000202] Formation of Bimolecular Assemblies by Spin Coating. MA1*2 and MA1*3 were obtained by iterative spin-coating of the solutions of PdCh(PhCN)2 and the mixtures of complexes 1 and 2, or 1 and 3, respectively. A 3.0 mM solution of PdCh(PhCN)2 in THF was used for the formation of MA1*2, whereas for the formation of MA1*3, a 4.0 mM solution of PdC12(PhCN)2 in THF was applied. An equimolar solution of complexes 1 and 2, or complexes 1 and 3, at a final concentration of 0.6 mM was used for the formation of MA1*2 or MA1*3, respectively. The PdChfPhCNTb solution was dropcasted on FTO / glass or ITO / PET substrates (2 cm x 2 cm, 4 cm x 4 cm or 6 cm x 6 cm) and these substrates were spun at 500 rpm for 10 s, followed by spinning at 1000 rpm for 30 s. Subsequently, the complex solutions were dropcasted after 80 s on the substrates, which were spun as above. The substrates were then immersed in acetone, and dried under a gentle stream of air. For the formation of MA1*2, the deposition cycle was repeated 18 times, whereas for the formation of MA1*3, the deposition cycle was repeated 12 times.[000203] Formation of Unimolecular Molecular Assemblies by Spray Coating. Spray coating was performed with an automatic Ultrasonic Spraying System (Sono-Tek) equipped with two ultrasonic nozzles (having 2-6 mm diameter spray areas, operating at 120 kHz), which weremounted onto an X-Y-Z movable scanner. The parameters of the spray-coating process are summarized in Table 1.Entry Spray parameters MA2b'cMA1” ‘2 cm x 2 cm 6 cm x S cm 2 cm x 2 cm 6 cm x 6 cm1 Nozzle to substrate distance (cm)a5.5 cm 5.5 cm 5.5 cm 5.5 cm2 Atomization (kPa)31.03 1.30 1.30 1.303 Flow rate (mL / min )a0.6 0.5 0.6 0.64 Nozzle speed (mm / s)B55 Number of passes 7 (Pd nozzle) 3 (Pd nozzle) 10 (Pd nozzle) 6 (Pd nozzle)7 (Fe nozzle) 3 (Fe nozzle) 5 (Fe nozzle) 3 (Fe nozzle)6 Repetition33 4 3 3 or 4aconditions were the same for both the nozzles.bTHF solution of PdCh(PhCN)2 (1.0 mM) was used.cCH^Ch / MeOH (1 : 1 v / v) solutions of complex 2 (0.2 mM) was used.dCJLCh / MeOH (1 : 1 v / v) solutions of complex 1 (0.3 mM) was used.[000204] Table 1. Spray coating parameters for the fabrication of electrochromic films using complexes 1 and 2.[000205] Formation of Molecular Assemblies (MAI) of Complex 1. MAI was obtained by automated ultrasonic spray coating of solutions of PdCh(PhCN)2 and complex 1. A THF solution of PdCl2(PhCN)2 (1.0 mM) and a CFFCF / MeOH (1 : 1 v / v) solution of complex 1 (0.3 mM) were used to form the coatings on FTO / glass substrates (2 cm * 2 cm or 6 cm * 6 cm) at an atomization pressure of 1.30 kPa. The nozzle-to-substrate distance was 5.5 cm, and the nozzle was moved in a preprogrammed pattern along the X and Y directions with a speed of 5 mm / s and with a flow rate of 0.6 mL / min at room temperature (~23 °C). The coating of 2 cm * 2 cm substrates was carried out as follows: The THF solution of PdCh(PhCN)2 (1.0 mM) was sprayed (10 passes), which was followed by spraying (5 passes) the C^Cb / MeOH (1 : 1 v / v) solution of complex 1 (0.3 mM). To generate the coating, this automated deposition was repeated 3x. The coating of 6 cm x 6 cm substrates was carried out as follows: The THF solution of PdC12(PhCN)2 (1.0 mM)was sprayed (6 passes), which was followed by spraying (3 passes) the CJbCh / MeOH (1 : 1 v / v) solution of complex 1 (0.3 mM). To generate the coating, this automated deposition was repeated 3x or 4 . The substrates were immersed in acetone for 30 s and were dried under a gentle stream of air. The spray coating parameters are summarized in Table 1.[000206] Formation of Molecular Assemblies (MA2) of Complex 2. MA2 was obtained by automated ultrasonic spray coating of solutions of PdC12(PhCN)2 and of complex 2. A THF solution of PdCl2(PhCN)2 (1.0 mM) and a CJLCh / MeOH (1 :1 v / v) solution of complex 2 (0.2 mM) were used to form the coatings on FTO / glass or on ITO / PET (2 cm * 2 cm or 6 cm * 6 cm) at an atomization pressure of 1.03 or 1.30 kPa, respectively. The nozzle-to-substrate distance was 5.5 cm, and the nozzle was moved in a preprogrammed pattern along the X and Y directions at a speed of 5 mm / s and with a flow rate of 0.6 mL / min at room temperature (~23 °C). The coating of 2 cm x 2 cm substrates was carried out as follows: The THF solution of PdC12(PhCN)2 (1.0 mM) was sprayed onto the substrate (7 passes), which was followed by spraying (7 passes) the CHzCb / MeOH (1 : 1 v / v) solution of complex 2 (0.2 mM). This deposition sequence was repeated 3* to generate MA2. The coating of 6 cm * 6 cm substrates was carried out as follows: The THF solution of PdCl2(PhCN)2 (1.0 mM) was sprayed (3 passes), which was followed by spraying (3 passes) the C LCh / MeOH (1 : 1 v / v) solution of complex 2 (0.2 mM). This deposition sequence was repeated 4* to generate MA2. The substrates were immersed in acetone for 30 s and were dried under a gentle stream of air. The spray coating parameters are summarized in Table 1.[000207] Fabrication of Laminated Electrochromic Devices without Storage Layer. A layered architecture was used to construct laminated sandwich cell based on MAI and MA4 on FTO / glass substrates and a MAI device was demonstrated on ITO / PET. The FTO-coated glass or ITO-coated PET substrates served as the working electrode, and a corresponding bare substrate as the reference and counter electrodes. A frame of 210 pm thick double-sided tape (3M 9088) was attached on the working electrode (2 cm x 2 cm, 4 cm x 4 cm or 6 cm x 6 cm for FTO / glass substrates and 2 cm x 6 cm for ITO / PET) leaving an exposed edge (1-2 mm) for silver paste or copper tape contacts. Contacts were also connected to an edge (1-2 mm) of the counter electrode. The two electrodes were placed with the two conducting faces facing each other. The electrolyte gel (70:20:7:3 wt% ACN:PC: PMMA:trifluoromethyl-sulfonamide lithium salt) was injected using a syringe between the two electrodes. The edges of the devices were sealed using epoxy glue. The device was then connected to a potentiostat and the electrochromic properties were investigated.[000208] Fabrication of Laminated Electrochromic Devices with PEDOT:PSS as Storage Layer. A layered architecture was used to construct laminated sandwich cell based on FTO / glassor ITO / PET substrates (2 cm x 2cm or 6 cm x 6 cm) coated with MAI and MA2 serving as working electrodes. PEDOT:PSS-coated FTO / glass or ITO / PET substrates (2 cm x 2 cm or 6 cm x 6 cm) were used as reference and counter electrodes, respectively. A PEDOT:PSS / isopropyl alcohol (1 : 1.4 v / v) solution was drop-cast onto FTO / glass or ITO / PET substrates (2 cm x 2 cm or 6 cm x 6 cm). Subsequently, the substrate was spun at 500 rpm for 10 s and then at 1000 rpm for 30 s. Next, the substrate was heated in an oven at 120 °C for 1 min. A frame of 210 pm thick double-sided tape (3M 9088) was attached on the working electrode leaving an exposed edge (1- 2 mm) for copper tape contacts. Contacts were also connected to an edge (1-2 mm) of the counter electrode. The two electrodes were placed with the two conducting faces facing each other. The electrolyte gel (90:7:3 wt % ACN / PMMA / lithium perchlorate salt) was injected using a syringe between the two electrodes.[000209] Fabrication of Laminated Electrochromic Devices with Au Coated Cu Grids as Storage Layer. A layered architecture was used to construct laminated sandwich cells based on MA2. The FTO / glass substrates coated with MA2 served as the working electrode, and gold- coated copper grids on PET was used as the counter electrode. The electrolyte solution (90:7:3 wt % ACN / PMMA / lithium perchlorate salt) was drop-cast onto the MA2-coated FTO / glass substrates (2 cm x 2 cm or 6 cm x 6 cm). The counter electrode was placed on MA2-coated FTO / glass with the gel electrolyte (90:7:3 wt % ACN / PMMA / lithium perchlorate salt) sandwiched between these substrates, which were held tight with an insulating two-sided, 210 / m thick double-sided tape (3M 9088) at each end.EXAMPLE 2Results - Metallo-Organic Assemblies as Electrochromic materials[000210] Three different metal ions and two bipyridine-derived ligands were used to demonstrate the scope of achievable colors, by utilizing only a small library of functional components - metallo-organic complexes 1-4. These complexes are known to undergo reversible one-electron redox processes. The Metal-to-Ligand-Charge-Transfer (MLCT) in the ground state (M2+) of these complexes is reflected in their high molar extinction coefficients (e > 2.1 x 104M’cm'1) and distinct colors (1: purple, 2: greyish, 3: orange, 4: bordeaux). Upon oxidation of the metal center (M2+— M3+), the MLCT gets prohibited and Ligand-Charge-Transfer (LCT) becomes dominant. This effect results in drastic reduction of light absorption in the visible region. The complexes have been designed to rapidly form on-surface molecular assemblies (MAs) by coordination with a late transition metal (Figure 7). The three or six vinyl-pyridyl moieties allow for rapid cross-linking with PdCh to generate polymeric 3D-networks with highchromophore densities. The precursor PdC12(PhCN)2 is used, as the two benzonitrile ligands are readily replaced by the pyridine-binding sites of complexes 1-4.[000211] Spin coating assisted formation of electrochromic films:[000212] The metallo-organic assemblies (MA1-MA4, MA1»2 and MA1»3) were prepared using iterative spin-coating of solutions of PdC12(PhCN)2 and the metal polypyridyl complexes (1-4) or equimolar mixtures of two different metal complexes (1*2 and 1*3) on transparent conductive oxides (TCOs). For the formation of MAI, MA2, MA4, and MA1*2 the deposition cycles were repeated 18 times. For the formation of MA3 and MA1*3 the deposition cycles were repeated 12 times. After each cycle, the films were immersed in acetone to remove materials, if any, and dried under a gentle stream of air (Figure 4).[000213] The MAs have been characterized by UV / Vis spectroscopy, angle resolved X-ray photoelectron spectroscopy (XPS), optical microscopy, focused ion beam (FIB) - scanning electron microscopy (SEM), atomic force microscopy (AFM), electrochemistry, and spectroelectrochemistry (SEC).[000214] Representative data for MAI is shown in Figures 8A-8E (The data for the other MAs is presented in appendix A). Figure 8A shows a set of ex-situ absorption spectra of MAI recorded after various deposition cycles (n < 18). Plotting the absorption intensity of the MLCT and at zma\ = 573 nm versus the number of deposition cycles corroborated the linear trend in growth behavior (Figure 8A, inset). The molecular density was found to be high and roughly estimated to be ~2.7 x io16molecules / cm2. The XPS spectrum of [MAI | FTO / glass] showed the two characteristic peaks of the 3d orbitals of Pd(II) at 337 eV (3 ds / 2) and 342 eV (3 ds / 2) the single peak of the Is orbital of N at 399 eV, and the two characteristic peaks of the 2p orbitals of Fe(II) at 708 eV (2p3 / i) and 720 eV (2pi / 2) (Figure 8B). The Pd / Fe ratio was found to be ~2.7, nearly twice the value for a network in which all the palladium centers are bound to two pyridine moieties of complex 1. This high palladium content and the observed N / Fe = 12.2 and N / Pd = 4.6 ratios indicate the inclusion of unreacted cross-linker, PdC12(PhCN)2. Angle-resolved XPS measurements indicated that the elemental distribution is uniform throughout the molecular assembly. The spatial homogeneity of the MAs was further illustrated by coating of the substrates of dimensions up to 6 cm x 6 cm with the purple MAI (Figure 8C). SEM measurements of a cross-section of [MAI | FTO / glass] was obtained by milling with a Focused Ion Beam (FIB). Prior to this milling process, the region of the cross-section was locally coated with a layer (0.6- 0.8 pm) of Pt in order to prevent damage caused by ion beam bombardment on to MAI (Figure 8D). The SEM image of the cross-section showed the glass support, FTO, MAI, and the Pt layer. The top view shows the grainy nature of MAI (Figure 8D). The thickness of the metallo-organicassembly was found to be -280 nm (18 deposition cycles) that is much higher compared to the interfacial roughness of [MAI | FTO / glass], No apparent defects were observed. AFM imaging showed a similar grain-like morphology with an average grain-size of 0.4 pm and a root-mean square roughness ( / Cms) of 40 nm for a scan area of 500 x 500 nm (Figure 8E).[000215] The electrochemical properties of the assemblies were evaluated using a three- electrode cell configuration consisting of [MA | FTO / glass, 10 Q / n], Pt and Ag / Ag+ wires as working, counter, and reference electrodes, respectively.[000216] Representative data for MAI is shown in Figures 9A-9B and Figures 10A-10B (the data for the other MAs is presented in appendix A). Cyclic voltammograms (CVs) of [MAI | FTO / glass] showed the redox characteristics for the Fe2+ / 3+couple, with a half-wave potential (Ey2) of 1.01 V and a peak-to-peak separation of 325 mV at a scan rate of 100 mV / s (Figure 9A). The charge density (Q) of 3.23 mC / cm2indicates a molecular density of 2.1 x 1016molecules / cm2, which is in good agreement with the UV / Vis data (2.7 x 1016molecules / cm2). Importantly, MAI was found to be stable for at least 1600 redox cycles (Figure 9A). An exponential dependence of the current on the scan rate and a linear dependence of the current on the square root of these scan rates were observed (Figure 9B), indicating a process controlled by slow diffusion. The calculated diffusion coefficients (Df) of MA1-MA4 correlate with the observed switching times. The diffusion coefficient (Df) can be related to the movement of the anions (PFe') in the MAs. The Df values of MAI, MA4 and the Df values of MA2, MA3 differ by about one order of magnitude. However, the molecular densities of MAI-4 are similar (-1 molecule / nm2). The additional three vinylpyridine groups for complex 2 is likely to hamper the diffusion of the anions and explains the lower Df value of MA2. The origin of the lower Df value and higher switching time for MA3 is unclear.[000217] Spectroelectrochemical (SEC) measurements revealed prominent differences in the absorbance spectra of the reduced (colored) and oxidized (bleached) states of all the MAs on FTO / glass (Figure 10A). Response times, defined as the time required to change the color to 95% of the ATmax, are: 1 s (MAI), 1.8 s (MA2), 6.8 s (MA3), 0.5 s (MA4), 0.5 s (MA1«2) and 4.3 s (3) and 8.5 s (1) (MA1*3) (for MAI). The two MAs (MA3 and MA1*3) containing the ruthenium complex 3 exhibited slower response times with respect to the applied potentials. These color changes are clearly visible to naked eye (Figure 10B). Interestingly, MA4 underwent a color-to-color transition; this assembly is dark red in the ground state (Os2+) and becomes yellow upon oxidation (Os3+) as a result of the strong absorbance band at kmax = 410 nm. The MAs have high contrast ratios (A%T) at the zma\ corresponding to the MLCT : 65% (MAI), 37% (MA2), 50% (MA3), 39% (MA4), 40% (MA1*2) and 57% (MA1*3) (For MAI, see Figure10B) These values are higher than the ratios that are reported for many electrochromic metal oxides, and are comparable to the contrast ratios of some of the best performing organic polymers reported. MAI, MA2, MA4 and MA1*2 have been operated under SEC for more than 500 redox cycles. The ruthenium complex 3 containing coatings are less stable.[000218] MAI and MA4 were integrated in laminated electrochromic devices. The devices setup consists of (i) [MA | FTO / glass] as the working electrode (bottom), (ii) FTO / glass as the counter and reference electrodes (top), (iii) a PMMA-based gel electrolyte, and (iv) Double-sided tape (3M 9088) as an insulating spacer. These devices have a low and practical operation potential range from -2.5 V to +3 V, switching times of 2 s (MAI) and 10 s (MA4). The electrochromic properties of the devices are evident from the absorption spectra and are clearly visible to naked eye. SEC measurements indicated that MAl-based device is stable for at least 75 redox cycles. The MA4-based device exhibited a color-to-color transition from bordeaux to yellow and is stable for at least 50 redox cycles. The yellow color is due to the strong absorption band at z max = 410 nm. These two devices have high contrast ratios at the zma\ of the MLCT band: 50% (MAI) and 32% (MA4).[000219] Therefore, a versatile approach towards the formation of electrochromic nanoscale assemblies on transparent-conductive oxides on both rigid and flexible substrates was demonstrated. The method is based on alternatively spin-coated layers of well-defined metal polypyridyl complexes and a palladium (II) salt to form electrochemically addressable films with a high chromophore density. By varying the central metal ion of the polypyridyl complexes (Os, Ru and Fe), their ligands and by mixing these complexes, coatings with a wide range of colors have been achieved. These coatings cover a large area of the RGB color space. The coloration intensities of these nanoscale films can be tuned by the number of deposition steps. The materials have very attractive ON / OFF ratios, electrochemical stabilities, and coloration efficiencies.EXAMPLE 3Ultrasonic spray-coating for the formation of electrochromic films[000220] Electrochromic coatings respond to a potential by changes in its absorbance or reflection. The modulation of the optical properties can be used for smart windows and display technology. However, the production of applicable metallo-organic assemblies in a large-scale industrial setting is a challenging task and requires the fulfillment of many parameters, including scalability, minimum deposition steps, high material utilization, and fast kinetics to allow for high throughput production. Similar to many studies about functional organic and polymer filmsand device formation, the formation of metallo-organic assemblies has been driven by function, high-performance, and stability, and not by the possibility for high-throughput production.[000221] In this disclosure, on-surface formation of functional metallo-organic assemblies has been developed using a fully automated spray-coating procedure. The process was optimized and resulted in the homogeneous coating of fluorine-doped tin oxide (FTO)|glass and of flexible indium-tin oxide (ITO)|polyethylene terephthalate (PET) with two metallo-organic assemblies (MAI and MA2). A commercially available Sono-Tek© automated set-up, with two nozzles was used to iteratively spray-coat THF solutions of PdCh(PhCN)2 (1.0 mM) and DCM / MeOH (1 : 1 v / v) solutions of complexes 1 (0.3 mM) or 2 (0.2 mM) to afford metallo-organic assemblies MAI and MA2, respectively (Figure 5). It is essential to first deposit the PdCh salt. The metal center is known to bind to the TCO and at the same time allows the attachment of complexes 1 or 2. Homogeneous coatings were obtained by using an atomization of 1.03 kPa - 1.30 kPa. The nozzle-to-substrate distance was 5.5 cm and the nozzles were moved several times for each solution along the X and Y direction with a speed of 5 mm / s and a flow rate of 0.6 mL / min. The alternating spraying of (PhCbfEPdCh and complexes 1 or 2 was repeated 3* or 4* depending on the substrate size (2 cm x 2 cm or 6 cm x 6 cm, respectively). At the end of the spray coating process, the purple MAI and gray MA2 were washed with acetone to remove any unbound material, and subsequently dried under a gentle stream of air to give the homogeneously colored TCOs (Figures 11A-11C).[000222] The MAs were further characterized in detail by scanning electron microscopy (SEM), focused ion beam (FIB)-SEM, atomic force microscopy (AFM), angle-resolved X-ray photoelectron spectroscopy (XPS), electrochemistry, and spectroelectrochemistry (SEC).[000223] The effectiveness of the spray coating and the function of the assemblies are further demonstrated by the excellent performances of the corresponding laminated ECDs. For fabrication of laminated ECDs, [MAl|FTO / glass], [MA2| ITO / PET], and [MA2|FTO / glass] were used as working electrodes. An example of a device with the purple MAI having an active surface area of 1.7 cm x 1.3 cm is shown in Figure 12A. FTO / glass is used as substrates for both electrodes, which are separated by a gel electrolyte (LiCICh / PMMA / ACN) and a spacer (doublesided tape).[000224] The counter FTO electrode is covered with a thin layer of PEDOT:PSS as an ionstorage layer. This electrochemically active layer is applied to enhance device stability because opposite redox reactions will occur at the working and counter electrodes during ECD operation. SEM analysis revealed that the spin-coated layer of PEDOT :PSS homogeneously covers the FTOsurface. Because of its low thickness of 90 ± 25 nm as derived from FIB-SEM measurements, this layer does not contribute significantly to the color of the devices.[000225] EC switching between the colored and transmissive states was observed using potential steps of -1.8 to +2.8 V with a pulse width of 20 s. Photographs of the ECDs demonstrate the consistency of the change in the color intensity upon 1500 redox cycles (Figures 12B and 12C). UV-vis measurements of this device clearly show the reversible intensity changes in the characteristic MLCT band at zma\ = 578 nm (Figure 12D). The spectroelectrochemistry (SEC) measurements show that the initial AT value of 38% decreases to ~31% (250 redox cycles) and remains stable for at least additional 750 redox cycles (Figure 12E). The corresponding ECD without PEDOT:PSS as an ion-storage layer is much less stable, as indicated by a decrease in AT from 49 to 20% after 100 redox cycles.[000226] To summarize, the high-quality coatings were used for device fabrication. For the assemblies, no other processing steps (e.g., preassembly in solution, thermal curing) are needed to acquire the desired redox and electrochemical activities. The thermally robust assemblies readily allow device integration in air- no strictly inert glovebox environment is required. The results indicate that the device performance can be further advanced by properly matching the properties of the gel electrolyte with the structure of the metallo-organic electrochromic coatings. A larger surface area results in higher resistance; therefore, a higher potential is required for device operation. Interestingly, metal grids as counter electrodes result in a large reduction in the potential window by several volts, which obviously results in lower energy loss as heat. A smaller potential window is also expected to reduce the possibility of device degradation by side reactions. The fully automated spray coating and the use of redox-active chemical components that can be prepared on a multigram scale are excellent indicators that these colored coatings can be produced in an industrial setting (i.e., R2R). Moreover, it can provide a relatively fast and versatile route to the on surface formation of diverse stimuli-responsive metallo-organic assemblies (including nanosheets). These materials are currently accessible by means of dip coating (LbL), assembly at liquid-liquid interfaces, or spin-coating procedures.EXAMPLE 4Formation of chiral nanostructures in solution[000227] In this work, the formation of chiral nanostructures in solution is shown, which are composed of racemic mixtures of metallo-organic complexes. The monomeric units of the complexes aggregate by utilization of TT-TC interactions, thanks to the extended 7t-system of the ligands arms. Repeat circular dichroism (CD) measurements show that the chiral supramolecularstructures are formed in solution, with random handedness: zero, positive and negative CD signals are observed for solutions with identical composition. High-performance liquid chromatography (HPLC) analysis demonstrate the presence of only two enantiomers in a 1 : 1 ratio. Therefore, chiral impurities can be excluded to mediate the unexpected formation of chiral supramolecular structures. The selective and random formation of an excess of one chiral supramolecular structures is evident for all the complexes, regardless of the used metal ion (Fe, Ru, Os) or the number of vinylpyridine moieties. Bipyridine (bpy) complexes, lacking these vinylpyridine moieties, do not form chiral structures in solution under the same conditions. This observation indicates that the driving force for the aggregation is TT-TC interactions between the vinylpyridine moieties. Control over the handedness of the formed nanostructures was demonstrated using seeding, which indicates that the aggregation process is a secondary nucleation process, also known as the “sergeant and soldiers” mechanism (Figure 2).[000228] Complex 2 is an octahedral iron complex with three bidentate bipyridine based ligands. Each ligand is equipped with two conjugated arms, with additional pyridine units in the edges. This molecular design leads to the formation of two enantiomers: A, and A. It was found that racemic solutions of 2, as was confirmed by chiral HPLC, contain nanostructures, with random handedness. The structural features of 2-nanostructures were studied by dynamic light scattering (DLS), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), TEM electron diffraction (TEM-ED), and cryogenic TEM. It was observed the formation of 2D sheets which is followed by stacking and rolling of these sheets to form twisted structures. Figures 13A-13F are SEM images of 2-nanostructures, where twisted structures are observed. The structures are of few hundreds nanometer size, which is in great agreement with DLS data, and are characterized with a twist, which makes them chiral. Two populations of particles are generally found, according to their morphology: the main population contains bow-tie like structures, with smooth surface. These particles tend to pack very closely to each other, indicates the existence of particle-particle interactions via their outer surface. The less-abundant population contains twisted rod-like structures, with rough surface, that seems to be composed of smaller units. These particles are found mainly isolated.[000229] The nanostructures were imaged additionally by atomic force microscope (AFM) and by cryogenic TEM. Figures 14A-14C shows particles of the same size with resembled shape, as was viewed by both methods.[000230] To investigate structural details, the twisted rod structures were characterized by TEM imaging: it turns out, as can be seen in Figures 15A-15E, that the roughness of the surface results in the fact that the nanostructures are composed of small cubic units. TEM electron diffractionreveals that these units are crystalline, where each cube was found to be a single crystal, but the overall agglomerate is not (Figure 15C). Crystals of complex 2 were obtained ex-situ using slow evaporation procedure, from a 1 : 1 v / v mixture of DCM and MeOH solution. The obtained crystals are needle-like shaped crystals. Single crystal X-ray analysis shows that molecules of complex 2 tend to pack in a racemic manner: the two enantiomers exist in the packing in 1 : 1 ratio. The molecules pack in a monoclinic unit cell, under P2(l) / c space group, in a way that the ligands arms are parallel to each other, in a distance of 3.8 A, which allows the formation of TT-TC interactions (Figure 15D). The electron diffraction data was correlated to the data from X-ray analysis, and found that although their morphology is different, it is possible that the cubic units are of the same space group as the ex-situ grown needle-like crystals. DFT calculations show that the most stable configuration for two complex molecules to aggregate, are of one enantiomer with a neighbor molecule of the same chirality (Figure 16), i.e. lambda tends to aggregate with lambda; and delta tends to aggregate with delta. Relative energies of four possible orientations of A-A molecules, and four possible orientations of A-A molecules are shown in Table 2:AA. 0.0 0.02 0.2 0.43 L0 L54 0.8 0.8AA 1 6.5 2.?2 4.6 6.24 2.2 3.4Table 2 - Relative energies (kcal / mol) if the A-A and A-A dimers.[000231] Circular Dichroism spectra of racemic solutions containing 0.6 mM complex 2 reveal that the solutions are optically active. Interestingly, the sign of the CD spectra for the racemate is different from batch to batch: the obtained CD signals could be positive, negative or zero signals for different batches of the racemate, under identical assembly conditions, showing that chiral assemblies with different enantiomeric ratios were formed in each batch, randomly (Figure 15B) In order to further investigate that the chiral morphology of the nanostructures originates in the 7t-7t interactions of the ligands arms, the optical activity of nine more isostructural complexes with different metal centers were studied, and bidentate bipyridine based ligands: Complex 2’, which is the hydrogenated form of complex 2, so its ligands are non-conjugated; Complexes 1, 3 and 4, that are designed to have iron, ruthenium and osmium as the metal centers,respectively, and three conjugated arms with pyridine units in the edges; Complex 4’, which is the hydrogenated form of complex 4, and therefore its ligands are non-conjugated; and complexes 5-8, which are a series of bipyridine complexes that will serve mainly as control systems (Figures 6A-6C). Complexes 1, 3 and 4, that their ligands are conjugated, and behave similarly to complex 2: racemic solutions of these complexes are optically active and can give rise to a positive or negative CD signal, randomly (Figure 17B). The rest of the complexes, however, show no optical activity, as expected (Figure 16).[000232] To further confirm the role of TT-TC interactions in the formation of these chiral structures, crystals of complex 2’ were obtained ex-situ using slow evaporation procedure, from a 1 : 1 v / v mixture of DCM and MeOH solution. Single crystal X-ray analysis shows that molecules of complex 2’ pack in a triclinic unit cell, under -7 space group, with high degree of disorder, unlike the ordered structure of the conjugated complex 2. Moreover, SEM imaging of complex 2’ show no aggregation (Figures 19B-19D).[000233] Claiming that a process is completely random is a challenging task. For this purpose, the effect of external forces on the formation of the chiral nanostructures has been investigated. Two types of external forces were examined: vibrational forces, by sonication, and shearing forces, by stirring. Two batches were prepared under identical conditions. Sample of the first batch was exposed to ultrasonic waves for 10 s, ten times. After each sonication, a CD spectrum was recorded (Figure 20A, squares). Sample of the second batch was stirred using tabletop shaker for 10 s (with no addition of a magnet), ten times, where after each stirring, a CD spectrum was recorded (Figure 20B, circles). Furthermore, these experiments were repeated with additional two identical batches, for further confirmation (Figure 20A, up triangles; Figure 20B, down tringles). The CD signal of the solution remains the same as it was, which means that the structures are durable and are not affected by the applied external forces, or that the signal changes, which indicates that the structures are fragile upon agitation, and free to reform with random handedness. The results in Figures 20A-20C show that indeed the structures fall apart and reform randomly. The reformation process was monitored by dynamic light scattering (DLS): DLS spectrum was recorded before sonication of a 0.6 mM ACN solution of complex 2 (Figures 21A-21B). Then the solution was sonicated for 10 s, and a spectrum was recorded immediately after the sonication. No peak was observed (Figures 21A-21B). At this point, the solution was kept at room temperature, within the DLS instrument, and a spectrum was collected every five minutes. As can be seen in Figures 21A-21B, a peak that correlates the nanostructures size has retrieved its initial intensity (from before the sonication) about ten minutes after thesonication had occurred (Figures 21A-21B: after 5 min, blue trace; after 10 min, green trace; after 15 min, purple trace; after 20 min, orange trace).[000234] Controlling the handedness of the randomly formed chiral nanostructures is not trivial. The handedness of the formed structures was controlled using seeding. Identical racemic solutions of complex 2 were prepared in the presence of no, positive or negative seed. Figure 22A shows the CD signal at 589 nm for a collection of 24 samples that were prepared without the presence of a seed: 17 out of the 24 samples gave rise to a negative signal, while 7 of them gave rise to a positive signal. When a negative seed was in use, ten out of the ten samples gave rise to a negative CD signal (Figure 22B). When a positive seed was in use, ten out of the ten samples gave rise to a positive CD signal (Figure 22C). In some embodiments the one- handedness is formed when the 2D sheets began to fold, then subsequent folding direction would follow that handedness because of cooperative interactions. The initial folding direction is randomly determined, which leads to different CD spectra each time.[000235] The initial steps of the aggregation are shown by cryo-TEM: two-dimensional sheets, which roll over to form the twisted nanostructures were observed (Figures 23A-23E). Based on the cryo-TEM images and the results presented above, the following mechanism is operating: at the first stage, 7t-7t stacking interactions between ligands of adjacent molecules allows the formation of small crystalline cubic units. Later, these units come closer, and aggregate to form 2D sheets. Finally, these sheets roll to form chiral twisted structures (Figure 24).[000236] To summarize, racemic mixtures of octahedral iron, ruthenium and osmium complexes are shown to be optically active. The chirality of these complexes solutions does not originate in its molecular composition, rather in its supramolecular chiral arrangement. It is shown that complex 2 molecules pack in a crystalline form, via utilization of TT-TC interactions. These crystalline units tend to aggregate to form 2D sheets, which later roll over to form chiral twisted nanostructures. The handedness of the structures is determined by the first aggregate that is formed. The probability for the formation of left-handed structures versus the right-handed ones is equal, therefore without the presence of a pre-formed seed, the process is completely random and zero, positive or negative CD signals can be obtained for solutions with identical composition. The chirality of the system discussed above is a result of the supramolecular arrangement, and not enantiomeric excess or enantio-pure composition. Meaning, while the molecules pack in a racemic achiral fashion, their supramolecular structure has a chiral morphology. This study is an important step towards further understanding the relationship between molecular chirality and supra molecular chirality, self-assembly processes, and symmetry breaking.EXAMPLE 5Electrochemically responsive chiral films[000237] The formation of chiral films using racemic solutions of octahedral complexes of iron and osmium are now shown. Here the nanostructures maintain chiral features when incorporated in three-dimensional coordination networks. The formed films are chiral and electrochromic, which enables modification of their characteristic UV / Vis signal, as well as their CD signal, upon oxidation or reduction. The spectral changes originate from changes in the electronic state of the system rather than its structural configuration, which allows addressing the system in its solid state.[000238] Films of iron complex 2 and its hydrogenated form 2’ are fabricated, as well as films of osmium complex 4 and its hydrogenated form 4’ by spin-coating. The same spin-coating deposition method that was used for the formation of MA2 and MA4 is used, to form their equivalent non-conjugated assemblies MA2’ and MA4’. The metallo-organic assemblies (MA2, MA2’, MA4, MA4’ ) were prepared using iterative spin-coating of solutions of PdC12(PhCN)2 and the metal polypyridyl complexes (2, 2’, 4, 4’) on commercially available Fluorine-doped tin oxide (FTO) supported on glass substrates, and on quartz substrates. First, tetrahydrofuran (THF) solution of PdCl2(PhCN)2 (3.0 mM) is drop-casted on the freshly cleaned substrate which was subsequently spun at 500 rpm for 10 s and then at 1000 rpm for 30 s. This layer is used for successive binding of the polypyridyl complexes. After 80 s, the PdCh-modified substrate was, without washing, exposed to a solution of dichloromethane (DCM) : methanol (MeOH) (1 : 1 v / v) of the corresponding complex. The deposition cycles were repeated 18 times. After each cycle, the films were immersed in acetone to remove physisorbed materials, if any, and dried under a gentle stream of air.[000239] The MAs have been characterized by UV / Vis spectroscopy, circular dichroism (CD) spectroscopy, angle resolved X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) - scanning electron microscopy (SEM), atomic force microscopy (AFM), electrochemistry, and spectroelectrochemistry (SEC).[000240] The optical properties of the four molecular assemblies that were formed are presented in Figures 26A-26B. Figure 26A and 26B show absorption spectra of MA2 versus MA2’ and MA4 versus MA4’, respectively. When measuring the CD of surfaces, one must eliminate linear effects, i.e. linear dichroism or linear birefringence, to obtain a true CD spectrum. This is enabled by measuring the surface at four different orientations, and averaging the obtained signals. This method takes advantage of the fact that the linear effects contribution to the CD signal is expressed by trigonometrical functions, which can be eliminated by positioning the sample atcertain angles with respect to the light beam (Figures 25A-25B). First, the sample is measure at a random orientation facing the source of light (denoted as: 0 in-plane), then it is rotated by 90 degrees (denoted as 90 in-plane). At this point the sample is flipped backwards with respect to the source of the light (denoted as 90 out-of-plane), and finally it is rotated again by 90 degrees (denoted as 0 out-of-plane). Figure 25B shows representative data of MA4, measured at four different orientations, and the quaternary sum of these signals, which is the true CD spectrum. The data that is presented in Figure 26A-26D is after the elimination of linear effects, using the described measuring technique. MA2 was found to be chiral, thanks to preservation of the chiral nanostructures that are formed in a solution of 2, during the formation of the assembly. The same was observed for MA4 (Figures 26C-26D).[000241] Complexes 2’ and 4’, on the other hand, lacks the conjugated systems of the ligands arms, therefore their solutions do not contain any chiral objects. As a result, assemblies MA2’ and MA4’ are not chiral, as can be seen in Figures 26C-26D. Since the handedness of the nanostructures that are formed in solution is random, and can give rise to positive or negative CD signals, so as films thereof. Figure 26A shows identical absorbance spectra for two different 2-based films (grey and turquoise traces) with opposite corresponding CD spectra (Figure 26C, grey and turquoise traces). The same is observed for two different 4-based films: Figure 26B shows identical absorbance spectra for two different films (red and bordeaux traces) with opposite corresponding CD spectra (Figure 26D, red and bordeaux traces). Assemblies for MA2’ and MA4’ are reported. The XPS spectrum of [MA2’ | FTO / glass] showed the two characteristic peaks of the 3d orbitals of Pd(II) at 337 eV (3d5 / 2) and 342 eV (3d3 / 2), the single peak of the Is orbital of N at 399 eV, and the two characteristic peaks of the 2p orbitals of Fe(II) at 708 eV (2p3 / 2) and 720 eV (2p 1 / 2) (Figures 27A-27B). Table 3 shows XPS-derived elemental ratios for MA2’ (M=Fe) and MA4’ (M=Os) at two take-off angles:Table 3 - XPS-derived elemental ratios.[000242] The Pd / Fe ratio was found to be ~2.8, which fits the expected value for a network in which all the palladium centers are bound to the six pyridine moieties of complex 2. Angle-resolved XPS measurements indicate that the elemental distribution is uniform throughout the molecular assembly: No significant changes in Pd / Fe, N / Fe, N / Pd ratios were observed when the signal was collected at a take-off angle of 6 = 0° (normal) and Q = 50°. The spatial homogeneity of the MAs was studied by microscopy imaging. AFM imaging showed a grain-like morphology with an average grain-size of 0.15 / m and a root-mean square roughness (Arms) of 60 nm for a scan area of 5 / m x 5(Figures 28A-28D). SEM measurements of a cross-section of [MA2’ | FTO / glass] was obtained by milling with a Focused Ion Beam (FIB) (Figure 28A-28D). The SEM image of the cross-section showed the glass support, FTO, MA2’, and a Pt layer that was used to prevent damage caused by the ion beam bombardment. The top view shows the grainy nature of MA2’, which is in great agreement with the AFM findings. The thickness of the metallo-organic assembly was found to be -280 nm (18 deposition cycles). No apparent defects were observed. The same set of data regarding [MA4’ | FTO / glass] can be found in Figure 27A- 27B and Figures 28A-28D.[000243] The metal complexes that serve as the main components in the assemblies are known to undergo reversible one-electron redox processes. The Metal-to-Ligand-Charge-Transfer (MLCT) in the ground state (M2+) of these complexes is reflected in their high molar extinction coefficients (2: e = 3.63 x 104 M^cm'1; 2’: e = 1.14 x 104 M^cm'1, 4: e = 2.1 x 104 M^cm'1; 4’: e = 1.2 x 104 M^cm'1) and distinct colors (2: greyish, 2’: pink, 4: Bordeaux, 4’: Khaki). Upon oxidation of the metal center (M2+— M3+), the MLCT gets prohibited and Ligand-Charge- Transfer (LCT) becomes dominant. This effect results in a drastic reduction in the light absorption by these complexes in the visible region. As MA2 and MA4 are chiral, it was found that upon oxidation, the CD signal of the assembly can be varied, in addition to the abovementioned changes of UV / Vis light absorption.[000244] The electrochemical (EC) properties of assemblies MA2 and MA4 and their hydrogenated equivalent assemblies were evaluated using a three-electrode cell configuration consisting of [MA | FTO / glass, 10 Q / n], Pt and Ag / Ag+ wires as working, counter, and reference electrodes, respectively. EC measurements of MA2’ reveal a reversible process, with peak to peak separation of 0.6 mV that is observed in the cyclic voltammogram (CV) of [MA2’ | FTO / glass], The half-wave potential (EU) of [MA2’ | FTO / glass] was found to be 0.71 V, which is lower than the value known for its equivalent conjugated system (1.0 V) (Figure 29A). An exponential dependence of the current on the scan rate and a linear dependence of the current on the square root of these scan rates were observed (Figures 29B) indicating a process controlled by slow diffusion. The same is known for [MA2 | FTO / glass], The diffusion coefficients (Df) of MA2, and MA2’, related to the movement of the anions (PFe') into the MAs,were derived from the Randles-Sevcik equation: For the oxidation of MA2’, Df ,oxof 2.12 x 10"9cm2 / s was found, while for the reduction, Df, red is 1.92 x 10'9cm2 / s. These values are an order of magnitude lower than the ones that are known for [MA2 | FTO / glass], which can indicate that the conjugated nature of the ligands of complex 2 facilitates the electrochemical processes occurring in the assembly.[000245] Different case was revealed when the EC properties of [MA4’ | FTO / glass] were investigated: Cyclic voltammograms (CVs) of [MA4’ | FTO / glass] show the redox characteristics for the Os2+ / 3+couple, with a half-wave potential (Ey2) of 0.73 V and a peak-to- peak separation of 142 mV at a scan rate of 100 mV / s (Figure 30A). However, unlike if the case of the equivalent MA2-MA2’ system, the non-conjugate nature of the hydrogenated form of complex 4’ seems to have no effect the electrochemical processes within the film: the diffusion coefficients for MA4’ are similar that of MA4: Df ,ox= 3.37 x 10'8cm2 / s and Df, red = 3.40 x 10'8cm2 / s were derived from the dependence of the scan rate root on the current (Figure 30B).[000246] SEC measurements reveal prominent differences in the UV / Vis absorbance spectra of the reduced (colored) and oxidized (bleached) states of all MA2, MA2’, MA4 and MA4’. However, as they differ with respect to chirality, prominent differences in the CD spectra were observed only in the case of MA2 and MA4 (Figures 31A-31F). Moreover, as was explained before, films with positive or negative CD signals can be obtained. Figures 31A and 31D present spectroelectrochemistry measurements for films that give rise to positive and negative CD signal of MA2, and MA4, respectively.[000247] The optical switching is measured by the difference between the CD signals of the reduced state and the oxidized state. In order to evaluate the contrast ratio of MA2, MA2’, MA4 and MA4’, double-potential steps chronoamperometry has been used: Potential steps of 0.4 V and 1.8 V were applied for the reduced and oxidized states of MA2, respectively, while for MA2’ steps of 0.4 V and 1.6 V were applied. For MA4, and MA4’ steps of 0.4 V and 1.2 V; and 0.2 V and 1.4 V respectively, were applied. The transmittance values of the MAs were monitored in situ, while applying the potential, at zma\ = 589 nm for MA2, at zma\ = 535 nm for MA2’, at zma= 510 nm for MA4, and at zmax= 500 nm for MA4’. The contrast ratio under polarized light is defined as the difference between the CD signal of the reduced state and the CD signal of the oxidized state. MA2 exhibits a contrast ratio of up to 5 mdeg, while MA2’ show no response in its CD spectrum. MA4 exhibits even a higher contrast ratio of up to 10 mdeg, while MA4’ shows no response (Figures 32A-32D). The response time, defined as the time required to change the color to 95% of the ATmax, are: 2 s (MA2), 20 s (MA2’), 0.5 s (MA4) and 5 s (MA4’) (Figure 29A-29F and Figures 30A-30F). This finding correlates with the diffusion coefficients and theEC behavior that are described above. The color changes that are associated with the redox reactions are clearly visible to naked eye (Figures 31C and 31F; photos).[000248] It has been shown that spin-coating racemic mixtures of octahedral iron and osmium complexes on TCOs, results in the formation of chiral films. These chiral films, which are also electrochromic, obtain CD signals, which can be modified by applying external field, and exhibits strong contrast ratio. Therefore, this system is unique in the sense that its CD signal, as well as its UV / Vis signal, can be modified by external stimuli, at the solid state.[000249] Figures 43A-43E show SEC spectra for electrochromic chiral films.[000250] Figure 44A-44B shows UV-Vis and Circular dichroism (CD) of the chiral complex: 1(A) - TRISPHAT (A). Figure 44A shows Uv-Vis of 0.01 mM (bottom trace) and 0.02 mM (upper trace) DCM solution of the 1(A) - TRISPHAT (A). Figure 44B shows a CD spectra of 0.01 mM (inner trace) and 0.02 mM (outer trace) DCM solution of the 1(A) - TRISPHAT (A). CD spectra indicate the formation of homochiral 1(A) - TRISPHAT (A).[000251 ] Figures 45A-45C show that chirality maintained on the surface as well after assembly formation: transfer of chirality from solution to surface. Figures 45D-45F show that the chiral films are stable for at least 1000 cycles. Laminated devices were also tested, and showed that the devices maintained 82% of initial AT even after 700 cycles.[000252]EXAMPLE 6Synthesis of complex 1 (A) - TRISPHA T (A)[000253] Reference is made to Figure 34 showing a synthetic route to prepare complex 1 (A) - TRISPHAT (A) from ligand LI.[000254] A suspension of the (E)-4-methyl-4'-(2-(pyridin-4-yl)vinyl)-2,2'-bipyridine LI (0.3 mmol, 3 eq. ) in water (10 mL) was added to a solution of FeC12 -4H2O (0.1 mmol, 1 eq. ) in water (1 mL). The solution was then stirred for 2 h, with occasional warming to 50 °C (every 30 min). After that, 10 mL of DCM was added to the purple solution. Initially, the DCM layer remained colorless, and the water layer was purple, indicating all the complex was in the aqueous layer. Then, a DCM solution (5 mL) of A-TRISPHAT tetrabutylammonium salt (0.2 mmol, 2 eq.) was added. Immediately, the purple color started to appear in the DCM layer. Next, solvent extraction was performed, and the DCM layer was collected. The organic layer was evaporated, and the purple solid was isolated, which was washed with 5 mL methanol followed by 10 mL diethyl ether to obtain the desired compound (Yield = 65%).[000255] 1 (A) - TRISPHAT (A).[000256] 'H NMR (500 MHz, DMSO): 8 9.08 (bs, 3H), 8.85 (bs, J = 9.1 Hz, 3H), 8.71 (d, J = VIA Hz, 6H), 7.98 - 7.53 (m, 15H), 7.53 - 7.30 (m, 6H), 7.25 - 7.19 (m, 3H), 3.14 (bs, 9H). 'H NMR data showed enantiodifferentiation of the cation.[000257] ESI-MS: 437.6574 for [M]2+, where M has the molecular formula of [Cs4H45N9Fe], Additionally, 1643.8890 for dictation with one counter ion [(M2+) + [(TRISPHAT)'}]+.[000258] FTIR (in cm'1): 1610, 1594, 1445, 1390, 1298, 1241, 992, 816, 717, 667, 648, 613, 587, 544.[000259] UV-Vis:max= 562 nm in DCM.[000260] Cyclic voltammetry: EQX= 0.98 V, ERed = 0.92 V, E1 / 2 = 0.95 V (Using 0.6 M [nBu4NPFe] electrolyte in ACN. (Working electrode: FTO / glass, Counter electrode: Pt wire, Reference electrode: Ag / Ag+).EXAMPLE 7Switchable chiral-optical and electrochromic properties with a mixture of two enantiomers [000261] Materials that exhibit both switchable chiral-optical and electrochromic properties are provided herein. The preparation of enantiomerically pure metal complexes and the formation of electrochromic films that are chiral are provided.[000262] The complexes use herein consist of a mixture of two enantiomers (A and A), as unambiguously shown by single-crystal X-ray diffraction measurements (Figures 35A-35B). Control of the handedness of the complexes, leads to design of chiral electrochromic films and devices. Preparative chiral HPLC is an option to separate the enantiomers. In various applications there is no need for certain concentrations, formation of aggregates, seeding and so on when chiral anions are used. Figure 35A-35B shows the delta and lambda isomers, they are in equilibrium. Adding a chiral anion changes the equilibrium and one of the isomers will be dominant. Needless to say, the A and A enantiomers should be stable and not undergo racemization after separation (Ray -Dutt twist) (Figure 36). Os-N and Ru-N bonds are stronger than Fe-N bonds. Therefore, osmium and ruthenium complexes could be suitable for separation by preparative chiral HPLC, but the amount of material that can be obtained is not very high. The torsional twists within iron bipyridyl complexes have a low kinetic barrier in solution at room temperature due to the lability of the Fe-N bonds. The lability of these bonds would result in the formation of racemic mixtures and no optical activity. The present approach to control thin film chirality is to use chiral counter anions such as TRISPHAT to facilitate selective precipitation or crystallization and shift the configurational equilibrium. Diastereomeric interactions with enantiopure counterions can result in the desired A and A complexes with a high enantiopurity(Figures 36 and 37A-37E). For [Fe(dimethyl-bpy)3]2+with enantiopure TRISPHAT as counterions in apolar CHCh, the formation of contact ion pairs with preferential homochiral association leads to a very high diastereomeric excess (d.e. > 96%). Therefore, TRISPHAT and other enantiopure counterions will be used to prepare electrochromic complexes having diastereomeric excesses. For example, the exchange of the PFe' counter ions of the iron complexes (1,2) can be achieved by reaction in a solution of these complexes with a few equivalents of A-TRISPHAT tetrabutyl-ammonium salt, followed by recrystallization. The optical activity (circular dichroism; CD) of such complexes is expected to intensify with decreasing solvent polarity because of the closer contact between the chiral counterion and the metal complexes. Electrochiroptical films will be assembled on transparent and flexible indium tin oxide (ITO)-coated polyethylene terephthalate (PET) substrates (30 Q / cm2, 6 cm ' 6 cm). Iterative spin coating or spray coating of solutions of metal salts (e.g., ZnCL, Cu(NOs)2, and FeCh) and the enantiomerically pure electrochromic complexes will be used for fabricating the films. The metal salts will coordinate to the vinylpyridyl groups of the complexes, forming a 3D network. These new films will be fully characterized using a combination of analytical tools including circular dichroism (CD) spectroscopy, electrochemistry, and polarized light spectroelectrochemistry (PL-SEC). Cyclic voltammetry (CV), a powerful electrochemical technique, will be used to investigate the reduction and oxidation processes of the surface-bound metallo-organic assemblies. The excess of the achiral counterions of the electrolyte solution (e.g., PFe-) might replace the chiral counterions of the electrochromic complexes. XPS measurements can determine whether an exchange of counterions occurs. However, this seems unlikely, because the large chiral counterions are probably trapped inside the 3D metallo-organic assembly. Even if such an exchange takes place, the electrochromic complexes are locked by the metal salts into a specific configuration that prevents the Ray -Dutt twist (Figure 36). Oxidation of the electrochiroptical films (M2+ / 3+) is expected to result in bleaching their intense metal-to- ligand charge transfer (MLCT) bands with a concurrent reduction in the CD signal. The electrochiroptical films will be integrated as optical modulators into prototype devices. A straightforward set-up demonstrating the diverse electrochiroptical properties consists of two parallel devices with opposite chirality (A and A) in the path of polarized light, as shown in Figures 38A-38D. Electrochemically addressing the metal oxidation states will bring about drastic changes in the light absorption and in the rotation of the polarized light. The versatility and scope of this proposed approach to produce electrochiroptical switches will be demonstrated by using enantiomerically pure ruthenium, osmium, and iron complexes that are iso-structural. This triad of iron, osium, and ruthenium complexes is electrochemically addressable at differentpotentials as layers in one film, allowing a wide range of potential electrochemical input-optical output combinations, as indicated in the tables (Figures 38E-38F). Such materials can be used for low-voltage chiral electrochromic display applications using circularly polarized transmission.[000263] In one embodiment, the term “a” or “one” or “an” refers to at least one. In one embodiment the phrase “two or more” may be of any denomination, which will suit a particular purpose. In one embodiment, “about” or "approximately" may comprise a deviance from the indicated term of + 1 %, or in some embodiments, - 1 %, or in some embodiments, ± 2.5 %, or in some embodiments, ± 5 %, or in some embodiments, ± 7.5 %, or in some embodiments, ± 10 %, or in some embodiments, ± 15 %, or in some embodiments, ± 20 %, or in some embodiments, ± 25 %.[000264] Those skilled in the art to which this invention pertains will readily appreciate that numerous changes, variations, and modifications can be made without departing from the scope of the presently disclosed subject matter, mutatis mutandis.

Claims

1. CLAIMS1. A chiral film comprising: chiral structures comprising at least one metal-coordinated organic complex; and at least one metal linker interspersed within the film.

2. The film of claim 1 wherein the chiral structures comprise pi-pi stacking.

3. The film of claim 1 wherein the metal -coordinated organic complex comprises bipyridine-based conjugated ligands comprising one or more unsaturated moieties bound to pyridine groups.

4. The film of claim 3 wherein the unsaturated moieties are selected from: C=C, C=C, C=N, and N=N, or a combination thereof.

5. The film of claim 1 wherein the chiral structures are crystalline.

6. The film of claim 1 wherein the chiral structures are in a form selected from: sheets, folded sheets, rods, twisted rods, cuboidal, bowties, half bowties, cuboidal, pyramids, or a combination thereof.

7. The film of claim 1 wherein the film is electrochromic.

8. The film of claim 1 wherein the at least one metal -coordinated organic complex is a polypyridyl complex.

9. The film of claim 8, wherein the polypyridyl complex is represented by Formula I:whereinM is a transition metal selected from Mn, Fe, Co, Ni, Cu, Zn, Ti, C, Cr, Rh, or Ir; n is the formal oxidation state of the transition metal, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai to Ae each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula I via R19R19 each independently is selected from a covalent bond, H2C-CH2, HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2 -COO-, -CONH-, -CON(OH)-, -NR20-, - Si(R2o)2-, an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acidresidues, or ’Rxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2o)2, -CON(R2o)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2o)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.

10. The film of claim 6 wherein the polypyridyl complex is represented by Formula II:wherein n is the formal oxidation state of Fe, wherein n is 0-6;X is a counter ion; m is a number ranging from 0 to 6;Ri to Ris each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Ai, A3, and A5 each independently is a group of Formula III, or of Formula IV, linked to the ring structure of the complex of general Formula II via R19III IVR19 each independently is selected from a covalent bond, H2C-CH2, cis / trans HC=CH, C=C, N=N, HC=N, N=CH, H2C-NH, HN-CH2 -COO-, -CONH-, -CON(OH)-, -NR20-, -Si(R2o)2- an alkylene optionally interrupted by one or more heteroatoms selected from O, S, or N, phenylene, biphenylene, a peptide moiety consisting of 3 to 5 amino acid•W "N- vresidues, orRxand Ryeach independently is selected from H, halogen, -OH, -N3, -NO2, -CN, -N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H;Bi to B3 each independently is selected from H, halogen, -OH, -N3, -NO2, -CN, - N(R2O)2, -CON(R2O)2, -COOR20, -SR20, -SO3H, -CH=CH-pyridyl, -(Ci-Cio)alkyl, -(C2- Cio)alkenyl, -(C2-Cio)alkynyl, -(Ci-Cio)alkoxy, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein the (Ci-Cio)alkyl, (C2-Cio)alkenyl, (C2-Cio)alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl may optionally be substituted with halogen, -OR20, - COR20, -COOR20, -OCOOR20, -OCON(R2O)2, -(Ci-C8)alkylene-COOR2o, -CN, -N(R2o)2, -NO2, -SR20, -(Ci-C8)alkyl, -O-(Ci-C8)alkyl, -CON(R2o)2, or -SO3H; andR20 each independently is H, (Ci-Ce)alkyl, or aryl.

11. The film of claim 1 wherein the chiral structures have a size ranging between 10 nm to 100 pm.

12. The film of claim 1 wherein the wherein the metal of the at least one metal linker is selected from the group consisting of Zn, Os, Ru, Fe, Pt, Pd, Ni, Ir, Rh, Co, Cu, Re, Tc, Mn, V, Nb, Ta, Hf, Zr, Cr, Mo, W, Ti, Sc, Ag, Au, and Y.

13. The film of claim 1 wherein the at least one metal linker is selected from: Na2PdC14, (SO3H-3-Py)2Pd(Cl)2, or a combination thereof.

14. A device comprising: a substrate; the chiral film of claim 1 ; an electrolyte disposed on the chiral film; an ion storage layer disposed on the electrolyte; and a counter electrode in contact with the ion storage layer.

15. The device of claim 14 wherein said electrolyte is selected from:ACN / PC / PMMA / trifluoromethylsulfonamide lithium salt, polymethyl methacrylate (PMMA), propylene carbonate (PC), LiCF3SO3, LiBF4, Li2+2xZni-xGeO4 (LiSICON), glassy lithium phosphorus oxynitride (LIPON), and LiCIC or any combination thereof.

16. The device of claim 14 wherein said ion storage layer comprises any of the following selected from: polymers, copolymers, metal-organic polymer, coordination polymer,molecular film, metallic coating, transparent conducting oxides, metal oxides, metal fluorides, metal nitrides, metal sulfides, nanocrystalline metal oxides, mixed metals oxides, redox-active species, carbon-based materials, graphene-based materials, buckminsterfullerenes, nanotubes, 2D materials, biomolecules, nanowires, polymethyl methacrylate (PMMA), benzocyclobutene (BCB) based polymers, poly(3,4- ethylenedioxythiophene), poly(styrenesulfonate), conjugated dithiolenes, polyelectrolytes, organic salts, inorganic salts, quinone-based compounds, viologen- based compounds, antimony-doped tin oxide (ATO), pyridine blue (PB), polyaniline, polypyrrole, lithium cobalt oxide, lithium cobalt oxide, indium tin oxide, fluorine doped tin oxide, niobium oxide, molybdenum oxide, zinc oxides, aluminum oxide, nickel oxides, ceric oxide, metal doped nickel oxides, lithium doped nickel oxides, lithium doped titanium oxides, polymetal oxides, nanoparticles, metallic nanoparticles, nickel hexacyanoferrate, iron hexacyanoferrate, lithium hexacyanoferrate, sodium hexacyanoferrate, manganese hexacyanomanganate, halogen-doped metal oxides, lithium sulfide, lithium garnet, lithium phosphorous oxynitride, lithium manganese oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, sodium nickel chloride and activated carbon.

17. The device of claim 14 wherein said counter electrode comprises any of the following selected from: glass, doped glass, metal -oxide, indium tin oxide (ITO)-coated glass, fluorine-doped tin oxide (FTO)-coated class, silicon, doped silicon, zinc oxide (ZnO), Si(100), Si(l l l), SiCh, SiH, silicon carbide mirror, quartz, metal, metal oxide, mixture of metal and metal oxide, group IV elements, mica, graphite comprising intercalated metal cations, polymer, plastic, zeolite, clay, membrane, optical fiber, ceramic, metalized ceramic, alumina, electrically-conductive material, semiconductor, steel, and stainless steel, gold, silver, platinum, copper, zinc, aluminium or any combination thereof.

18. The device of claim 14 wherein the chiral layer is in the form of an array of pixels and / or patterned on the substrate.

19. The device of claim 14 further comprising a lamination.

20. The device of claim 14 wherein the chiral film is electrochromic.

21. The device of claim 14 for use in any of the following: smart windows, electrochromic windows, smart mirrors, optical filters, frequency doubling devices, spatial light modulators, pulse shapers, displays, signs, plastic electronics, lenses, and sensors.

22. A method of producing a chiral solution, the method comprising: providing a solution comprising at least one chiral anion; disposing at least one metal-coordinated organic complex in the solution thereby producing the chiral solution comprising chiral structures of the at least one metal-coordinated organic complex.

23. The method of claim 22 wherein the solution comprises any of the following selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols, aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones and diethyl ether or any combination thereof.

24. The method of claim 22 wherein the at least one chiral anion comprises a negatively charged functional group.

25. The method of claim 24 wherein the negatively charged functional group is selected from: phosphates (PO43), sulfonates (RS(=O)2O ), sulphates (SCU)2', carboxylates (RCOO-), borates (R4B") serinate ([CsEfcNCh]-), alanine ([CsEBNCh]-), tartaric acid ([CTHeOr,]2-), mandelic acid ([CsHsCE]-), aspartic acid (^EfcNCU]-), glutamic acid ([CsElsNCU]-), methionine ([CsEEiNChS]-), phenylalanine ([CgElnNCh]-), camphorsulfonate ([CIOHI504S]’), isoleucine ([CeElBNCh]-), ibuprofen ([C13H17O2D, leucine ([C6H13NO2]-), naproxen ([C14H13O3]-), valine ([CsElnNCh]-), serine ([CsEBNCE]-), cysteine ([CsEENChS]-), naproxenate ([C14H13O3D, proline ([CsEENCh]-), histidine ([CeEENsCh]-), tyrosine ([CgHnNOs]-), glutamate ([CsElsNCU]-), tryptophan ([C11H12N2O2D, threonine ([C4H9NO3D, L-Tartrate fl^EUOe]2’), D-Tartrate ([C4EUO6]2'), phenylalaninate ([CgEEoNCh]-), ibuprofenate ([C13H17O2]-), L-Malate ([C4H4O5]2'), D-Malate ([C4H4O5]2'), lactate ([C3H5O3]’), D-Lactate ([C3H5O3]’), mandelate ([CsEBCE]-), leucinate ([CeHnNCh]-), aspartate ([C4H5NO4D, phenylglycinate ([CsElsNCE]-), camphorate ([C10H15O4D, camphanate ([C10H15O4D, methioninate ([CsElnNChS]-), norbornane-2-carboxylate ([C7H11O2D, troponate ([C7H11O2D, cysteinate ([CsEfcNCES]-), alaninate ([CsEBNCh]-), isoleucinate ([C6Hi3NO2]"), valinate ([CsElnNCh]-), and tetrabutylammonium tris(3,4,5,6-tetrachlorobenzene- l,2-diolato-K2O1,O2)phosphorus(V) [(PCChCeCU)3-)] (=TRISPHAT), or any combination thereof.

26. The method of claim 22 wherein the at least one chiral anion comprises the deprotonated form of any of the following selected from: tartaric acid, mandelic acid, amino acids, lactic acid, camphor, sulfonic acid, or a combination thereof.

27. The method of claim 22 wherein the at least one chiral anion comprises any of the following selected from: chromophore, fluorophore, metal, boron-dipyrrom ethene (BODIPY), porphyrin, fluorene, azobenzene, stilbene, rhodamine, indocyanine, polycyclic aromatic hydrocarbons, at least one halide, electron withdrawing group, electron donating group, or a combination thereof.

28. The method of claim 27 wherein the electron withdrawing group is selected from: fluorocarbons, aldehydes, halogens, carbonyl, cyanides, nitro, sulfonic acid, carboxylic acid, ester group, amide group, nitroso group, or a combination thereof.

29. The method of claim 27 wherein the electron donating group is selected from: alkyl, allyl, vinyl, phenyl, alkylamino, alkoxy, amino, hydroxyl, thiol, ether, or a combination thereof.

30. The method of claim 27 wherein the polycyclic aromatic hydrocarbons are selected from: naphthalene, biphenyl, fluorene, anthracene, phenanthrene, phenalene, tetracene, chrysene, triphenylene, pyrene, pentacene, perylene, benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene, benzo[c]fluorene.

31. A chiral solution prepared by the method of claim 22.

32. A chiral solution comprising: a solution comprising at least one chiral anion; chiral structures dispersed within the solution; and wherein the chiral structures comprise at least one metal -coordinated organic complex.

33. A method of producing an electrochromic chiral film, the method comprising: e) providing a substrate; f) depositing a linker layer comprising at least one metal linker; g) depositing a chiral solution comprising chiral structures and a chiral anion, wherein the chiral structures comprise at least one metal-coordinated organic complex; andh) repeating steps (b) and (c) until a desired thickness is reached, forming a chiral film.

34. The method of claim 33 further comprising at least partly removing the chiral anion by exchange with achiral counterions, and wherein the electrochromic chiral film remains chiral.

35. The method of claim 33 wherein the achiral counterions comprise any of the following selected from: PFe', organic anions, pseudohalides, boron-based anions, hydride-based anions, halide anions, phosphorus-based fluoroanions, oxyanions, and oxide-based anions, or a combination thereof.

36. The method of claim 33 wherein the depositing is selected from: spin coating, dip coating, brush coating, roller coating, flow coating, drop casting, mill rod coating, chemical vapor phase deposition (CVD), roll-to-roll (R2R) processing, electropolymerization, printing, layer-by-layer deposition, organic powder coating, inkjet printing, spray coating, ultrasonic spray coating, blade-coating, physical vapor deposition (PVD), Meyer bar coating, or a combination thereof.

37. The method of claim 33 wherein the at least one metal linker comprises a metal salt.

38. The method of claim 37 wherein the metal salt is a metal -based coordination complex.

39. The method of claim 33 wherein the at least one metal linker has the general formula MXYL1L2; wherein M is metal;X is a halide counterion;Y is a halide counterion; andLi = L2 or Li L2;Li and L2 are one ligand with two binding groups wherein each binding group is the same or different.

40. The method of claim 39 wherein the M is: zerovalent, monovalent, bivalent or trivalent.

41. The method of claim 39 wherein M is selected from: Fe, Co, Zn, Ni, Pt and Pd.

42. The method of claim 33 wherein the at least one metal linker is selected from: PdCh, PdCh CFhCN PdCh(PhCN)2, PdCbfCxHn) where CxHn is cycloocta- 1,5-diene (cod) or abbreviated PdCh(cod), PdSO4, Pd(NO3)2, Pd(OAc)2, PdBn, Pd(OSO2CF3)2, Pd(BF4)2,PtCl2, PdC12(Sme2)2, PdBr2, PdBr2(CH3CN)2, PdBr2(PhCN)2, PdBr2(C8Hi2) where C8Hi2 is cycloocta- 1,5-diene (cod) or abbreviated PdBr2(cod), PdSO4, Pd(NO3)2,Pd(OAc)2, PdBr2, Pd(OSO2CF3)2.Pd(BF4)2, PdC12(olefm)nwith n = 1, 2 or 3, PdBr2(olefm)nwith n = 1, 2 or 3, PtC12(olefm)nwith n = 1, 2 or 3, PtBr2(olefin)nwith n = 1, 2 or 3, PtC12PtC12(CH3CN)2, PtCl2(PhCN)2, PtCl2(C8Hi2) where C8HI2is cycloocta- 1,5-diene (cod) or abbreviated PtCh(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtCl2, PtBr2(CH3CN)2, PtBr2(PhCN)2, PtBr2(C8Hi2) where C8HI2is cycloocta-l,5-diene (cod) or abbreviated PtBr2(cod), PtSO4, Pt(NO3)2, Pt(Oac)2, PtBr2, Pt(OSO2CF3)2, Pt(BF4)2, PtC12(Sme2)2, PtBr2(Sme2)2, CuSO4, CuCl2, Cu(OH)2, Cu(NO3)2, Cu(Oac)2, CuBr2, Cu(OSO2CF3)2, CU(BF4)2, CU(C6H5CO2)2, NiCh, NiCl2(CH3CN)2, NiCl2(PhCN)2, NiCl2(C8Hi2) where C8HI2is cycloocta- 1,5-diene (cod) or abbreviated NiC12(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2, Ni(BF4)2,NiC12, NiCl2(Sme2)2, NiBr2(CH3CN)2, NiBr2(PhCN)2, NiBr2(C8Hi2) where C8HI2is cycloocta- 1,5-diene (cod) or abbreviated NiBr2(cod), NiSO4, Ni(NO3)2, Ni(Oac)2, NiBr2, Ni(OSO2CF3)2,Ni(BF4)2, NiBr2(Sme2)2, NiC12(olefm)nwith n = 1, 2 or 3, NiBr2(olefm)nwith n = 1, 2 or 3, ZnCl2, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBr2, ZnC4HeO4, ZnSO4, Zn(Oac)2, ZnBr2(olefm)nwith n = 1, 2 or 3, ZnC12(olefm)n with n = 1, 2 or 3, K2PdCl4, K2PdCl6, Na2PdCl4, Na2PdCl6, K2PtCl4, K2PtCl6, Na2PtCl4, Na2PtCl6, FeCl2, FeBr2, Fe(NO3)2, FeSO4, FeBr2(olefm)nwith n = 1, 2 or 3, FeC12(olefm)nwith n = 1, 2 or 3, Fe(OAc)2or any combination thereof.

43. The method of claim 38 wherein the metal -base of the metal-coordinated organic complex is selected from: Os, Fe, Ru, Mn, Cu, Zn, Ni, Cr, Ti, V, Ir, or Rh.

44. The method of claim 33 further comprising cleaning and drying the chiral film after at least one step.

45. A method of producing a chiral solution, the method comprising: providing a solvent; disposing at least one metal-coordinated organic complex in the solvent, producing an approximately racemic solution; providing a chiral seed comprising a metal-coordinated organic complex; and disposing the chiral seed into the racemic solution thereby producing the chiral solution comprising chiral structures formed from the at least one metal- coordinated organic complex.

46. The method of claim 45 wherein the solvent is selected from: water, hydrocarbon solvents, aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated solvents, alcohols,aldehydes, ketones, glycol ethers, esters, and glycol ether esters, halogenated solvents, chlorinated hydrocarbons, brominated hydrocarbons, acetonitrile (ACN), benzonitrile, tetrahydrofuran (THF), n-methyl-2-pyrrolidone (NMP), isopropanol (IP A), acetone, ethanol, methanol, toluene, chlorobenzene, xylene, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), pentane, hexane, toluene, non-halogenated solvents, esters, ethers, ketones, and diethyl ether or any combination thereof.

47. The method of claim 45 wherein the racemic solution has a concentration ranging between 0.1 to 10 mM.

48. The method of claim 45 wherein the chiral seed is selected from: right-handed chiral seed to produce a right-handed chiral solution; or left-handed chiral seed to produce a left-handed chiral solution.

49. The method of claim 45 wherein the chiral seed is in the form of an aggregate, nanoparticle, crystal, flake, film or a combination thereof.

50. The method of claim 45 wherein the chiral seed has a size ranging between 10 nm to 10 pm.

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